CA1041343A - Process of forming yellow photographic images - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

This invention discloses a novel process for forming a dye image which comprises developing an image-exposed silver halide photographic emulsion layer by an aromatic primary amine colour developing agent in the presence of an (aromatic acyl) acetoamide compound which is substituted in the d-position by a diacylamino group. This latter compound is represented by the general formula (I) wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group, and Z is the non-metallic atom or atoms necessary to form, together with the moiety in the formula, a 4-, 5- or 6- membered substituted or unsubstituted ring. A photographic element containing this compound is also disclosed. These novel yellow-forming couplers are 2- equivalent yellow couplers and require only two moles of exposed silver halide to form one mol of methine dye.
These couplers are suitable for colour photography using the colour subtraction process and reduce the content of silver halide incorporated into the emulsion thereby improving the sharpness of the image obtained.

Description

~0~13~;3 B~CKGROUND OF THE INVF.NTION , 1. Field of the Invention The present invention relates to a process of forming a color photographic image and more particularly to a process of forming a color photographic image using a novel yellow-forming coupler.

2. Description of the Prior Art For the formation of a color photographic image by a subtractive color process, a step is utilized in which the silver halide grains in an exposed silver halide photographic emulsion layer are reduced by a developing agent, generally an aromatic ;~
primaxy amine compound, in particular an N,N-di-substituted p-phenylerlediaminic compound, and the oxidation product of the developing agent formed at the same time causes a coupling reaction with color-forming couplers to give cyan, magenta, and yellow images.
Each coupler used in the color developing process is a compound having a phenolic hydroxyl group, an anilinic amine .~ , .. . .
~o group, or an active methylene group which yields, by oxidative coupling with the aromatic primary amine developing agent, a ; dye capable of absorbing light in a visible wave length region.
A yellow dye image abqorbs a blue light component in a ; wave length region of from about 400 millimicrons to about 500 millimicrons. Known yel:Low-forming couplers include ~-keto- ~-,. , ~
aceto-acetic acid esters, ~-diketones, N,N-malondiamides, a- ,-acylacetamides, etc.

~mong these yellow-forming couplers, benzoylacetamide ;

~; type compounds have been widely used as good yellow-forming `~ 30 couplers in the field of color photography. Almost all of these , 1 ' ~

: : .
:. .
.' . .
.. i, .. .. . . .. :

~O9L~3~3 1 yellow-forming couplers are 4~e~uivalent couplers, that is, couplers which require 4 mols of exposed silver halide as an oxidizing agent for forming one mol of azomethine dye. However, the incorporation of a large amount of silver halide in a photosensitive emulsion la~er is accompanied with disadvantages, ~' i.e., light scattering in the emulsion layer increases to reduce the sharpness of the image formed and the thickness of the emulsion layer increases to reduce the processing rate of the photographic light sensitive material. Furthermore, such a type of yellow-forming coupler also has the fault that the formation of the dye by the coupler is not completed in a color development which requires a strong oxidizing agent in a subsequent processing step.
In order to improve those faults, it has been proposed ~l, to use a so-called 2-equivalent yellow coupler, that is a ~ coupler which requires only two mols of exposed silver halide i to form one mol of methine dye.
,~ A 2~equivalent yellow coupler has the structure where ~; one of the hydrogen atoms of the active methylene group sub-stituted for by a coupling off or splitting off group. As . .
~i examples of such coupling oEf groups, a fluorine atom is .
described in U~S. Patent No. 3,277,155; a substituted phenoxy group in U.S. Patent No. 3,408,194; an acyloxyl group in U.S. Patent No. 3,447,928; a sulfoxyl group in U.S. Patent ~,. .
No. 3l4l5l652i and also the compound shown by the following formula / S2 ~Q
., ~: \CO _, ' ;~ .

in United States Patent Number 3,730,722.
".;
..
:- - 2 -' ~; , ,, U, ! . `.
.t . .
., ` .
... ... ~ . . ,. .. . . ;

:
~L09L13~3 1 The couplers disclosed in the above United States Patents and in U.S. Patents 3,265,506 and 3,253,924 also have groups analogous to Rl and R2 in the present invention, and serve to ; illustrate the wide class of groups which can serve as acceptable R~ and R2 groups in the present invention.
However, man~ of thcse known couplers have faults, i.e., they are insufficient in coupling reactivity, they give high color fog, the coupling activity of the couplers in photographic light-sensitive materials gradually reduces due to the instability oE the couplers themselves, they cause stain, the yellow dyes formed from such couplers are weak in preservation stability, and/or they are not easily produced. In short many of such couplers are not always satisfactory.

SUMMAR~ OF rrHE INVENTION

The first object of this inv~ntion is, therefore, to provide a novel yellow~forming coupler suitable for color ;~ photography usiny the color subtraction process.
The second object of this invention is to provide a - -process of forming a dye image by developing a silver halide photographic emulsion layer in the presence of such a ~vel~
yello~ f~ning coupler.
The third objec-t of this invention is to provide a color photographic light-sensitive material having a silver ~;
halide emulsion layer containing the novel yellow-f~r~ing coupler.
The fourth object of this invention is to provide a color developer containing such a novel yell~-forming coupler.
The fifth object of this invention is to provide a process of reducing the content of silver halide incorporated in a silver halide photographic emulsion by using such a novel yellow-forming coupler, thereby improving the sharpness of the :.: .

i ...

.
. ,.
:
:
;: . .. . . . . . .

~04~343 ::
1 photographic image obta}ned.
The sixth object of this invention is to provide a color photographic light-sensitive material suitable for ~uick color development processing using a blix bath containing a weak oxidizing agent and a silver complex salt-forming agent.
The seventh obj~ct of this invention is to provide a process of forming a yellow dye image having spectral absorption characteristics suitable for color reproduction by a subtractive color process which image has excellent stab.ility.
The foregoing objects are accomplished in accordance with the present invention by providing a photographic element and a method for the formation of dye images where a silver halide photographic emulsion is processed using an aromatic primary , . .
~;~ amino developer in the presence of an ~aromatic acyl) acetoamide i; compound substituted in the a-posi*lon by a diacylamino group.
; More particularly, the method according to the present invention involves processing a silver halide photographic emulsion with an aromatic primary amino developing agent, in ;~

the pre~sence of novel yellow-forming coupler having a diacyl-amino substitutent in the a--position thereo~ which may be represented by the following General Formula (I) . .
~,'.
H
s: R - c -- fH c ~,R2 ~' 0 = C/ \C = 0 General Formula (I) Z,~ .', .:
wherein R is an aryl group, R is an aryl group or a heterocyclic group, and Z i.s the ~on-metallic atoms necessary to form, together with the 0=C C-0 moiety in the formula, a 4-membered, 5-membered or 6-membered substituted or unsubstituted ,.~.: ~ .
~-- 4 ,.,, ,: .
... .
:. .
.,::
.' , ~ 04~3~3 ring. ~1, R2 and Z will have the same meaning in all formulae hereafter discussed unless otherwise indicated.
DESCRIPTIGN OF THE PREFERRED EMBODIMENTS :

In the above-described General Formula (I), the group Rl represents an aryl group such as a phenyl group or a substituted `~ phenyl group. The substituents which can be present on the phenyl group include, in addition to the monovalent substituents hereinafter described, divalent moieties which together with the phenyl nucleus form a condensed ring system ~ ~, in which A represents the atoms necessary to form an aromatic condensed ring system. Such aryl groups having a condensed ring system include naphthyl, quinolyl, iso-~uinolyl, chromanyl, ; ;
. -.
coumarinyl and tetrahydronaphthyl groups. General Formula (I) i; al~o includes those derivatives in which two residual groups ~' each of the same formula -~HCONHR2 : O=C ,C=O , .

are bound either to an arylene group, or two aryl groups combined `~
via a bivalent group. In such cases the coupler can be represented ~ by the following general formula: ;
....
Rl (COIHCONHR )2 '' ' ~N
~" ' O=C ,C=O ' .
~Z~
wherein R represents an arylene group or - Y - Y'-Y- wherein Y
.: , .
represents an arylene group and Y' represents a bivalent group.

Examples of such bivalent groups are -CH2-, -0~
, . . . .. .. .
-NHCONH- and the like.

~i`` The group R2 represents an aryl group such as a phenyl group or a substituted phenyl group. The substituents which can ~-~ - be present on the phenyl yroup include, in addition to the ~ - 5 -''.:.'`' ' .
. .:
, . . .

. .
'i''' ' ~0~3~3 1 monovalent substituellts hereinafter described, divalent moieties which together with th phenyl nucleus form a condensed ring system ~ ~ in which ~ represents the atoms necessary to form an aromatic condensed ring system. Such aryl group having ; a condensed ring system include naphthyl, quinolyl, iso-quinolyl, ehromanyl and coumarinyl tetrahydronaphthyl groups. General ~;' Formula (I), also include, those derivatives in which two residual groups each of the same formula RlCOÇHCONH- are bound .,: o=~=o either to an arylene group, or two aryl groups combined via a bi-; valent group. In such cases the coupler ean be represented by the following general formula:
(RlCOCHCON~I) 2R2 O=C ~C=O
; ~
: ~ _z, ; 2' ;; wherein R represents an arylene group, or -Y-Y'-Y-, wherein Y
represents an arylene group and Y' represents a bivalent group.
Examples of such bivalent groups are ~CH2-, -O-, -NHCONH- and the like.
The monovalent substituents on the phenyl nueleus of ~ the groups Rl and R2 ean be seleeted from a broad range of i~; residual groups. Sueh substituents include, or example, ;`~ halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl ~-:~ . . . .
groups, aryloxy groups, alkylcarbonyl groups, aryl earbonyl ; groups, alkylsulfonyl groups, aryl sulfonyl groups, carboxyl groups, thiocyano groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamide groups, amino groups, nitro groups, cyano groups, and hydroxyl groups, acyl groups, aryloxycarbonyl group, alkoxysulfonyl groups, aryloxysulfonyl group and sulEonamino .:
", . .

~,., .:, ,:
'`' ~
:; ' i !;

~04134~ ~ ~
1 group. The positions occupied by a hydrogen atom or atoms in these groups may be further su~stituted, i.e., a hydrogen atom or atoms can be replaced by a substituent giving rise to a sub-stituted group. The phenyl nucleus of the groups Rl and R2 is preferably substituted by one or more of the above-described substituents.
The phenyl group represented by the following formula is a preferred R group:
0 y ~
y 4 wherein Y4 and Y8 each represents a hydrogen atom, an alkyl group (Cl-C32) or an alkoxy group tcl-C32~, and Y5, Y6 and Y7 each represents a hydrogen atom, an alkyl group (Cl-C32), an alkoxy group (Cl-C32), an aryloxy group (such as phenoxy, tolyloxy, amylphenoxy, di-amylphenoxy, nonylphenoxy, methoxy-phenoxy, chlorophenoxy, naphthoxy, etc.), an amino group, an alkylamino group tCl-C32) or an acylamino group (Cl-C32).
The phenyl group represented by the following formula ~-is a preferred R group: ~
-:
5,, ~ y ~, ~',' y_~ .'~ .
,''.:' y~X '~
~,:. 1 ~s wherein X represents a halogen atom, an alkoxy group (Cl-C32~, .$ ;.~'~ an aryloxy group (Cl-C32), a di-substituted amino group (Cl-C32), 7 ` ' and Yl, Y2 and Y3 each represents a hydrogen atom, a halogen atom, an alkyl group (Cl-C32), an alkynyl gxoup tCl-C32), an alkoxy group tCl-C32), an aryl group (such as phenyl, tolyl, ; !
amylphenyl, di-amylphenyl, nonylphenyl, methoxyphenyl, chloro-; phenyl, naphthy:L, etc.), aryloxy (such as phenoxy, tolyloxy, , .
~ - 7 -. , .
.1.

:
: .. ,,, .. . :.:
: ~:.. , ., : . - . .- : ,.

10~343 :
1 amylphenoxy, diamylpheno~y, nonylphenoxy, methoxyphenoxy, ` chlorophenoxy, naphthophenoxy, etc.), alkylcarbonyl (Cl-C32), arylcarbonyl, alkylsulfonyl (Cl~C32), arylsulfonyl, carboxy, alkoxycarbonyl (C1-C32), carbamyl (C~-C3~), sulfo, sulfamyl ~Cl-C32), acylamino (Cl-C32~, ureido (Cl-C32), sulfonamide (Cl-C32), amino, nitro or cyano. The heterocyclic group which -;
may be represented by the group R2 is bound through a carbon atom of the heterocyclic ring to the residual group R
COIHCONH-O~C~ \ C=O

Z
This carbon atom is a member of the conjugated electron system of the ring, i.e., a carbon atom which thus exhibits an aromatic character. Such heterocyclic groups include those of the .
thiophene type, such as a 2-thiophenyl, a 3-thioph~nyl, a 2-benzothiophenyl, a 3-benzothiophenyl, a 2-naphthothiophenyl, a :,~. ~ . . ...

3-naphthothiopheny]., or a 3-thiophenyl group; those of the ;-furan type, such as a 2-furyl, a 3-furyl, a 2-benzofuranyl, a 3-benzofuranyl, a l-isobenzofuranyl or a 3-isobenzofuranyl ;~
group, those of the pyran type, such as a 3-pyranyl, a 4-pyranyl, a 5-pyranyl or a 6-pyranyl group; those of the chromene t.ype, such as a 3-chromenyl, or a 4-chromenyl group; those of the pyrrole type, such as a 3-pyrrolyl group; those o~ the pyrazole type such as a 3-pyrazolyl or a 4-pyrazolyl group; those of the pyridine type, such as a 2-pyridyl, a 3-pyridyl, a 4-pyridyl, a 2-quinolyl, a 3~quinolyl, a 4-quinolyl/ a l-isoquinolyl, a 3-isoquinolyl or a 4-isoquinolyl,group; those of the pyrazine type, such as a 2-pyrazinyl or a 2-quinoxalinyl group, those ;
of the pyrimidine type, such as a 2-pyrimidinyl, a 4-pyrimidînyl, a 5-pyrLmidinyl, a 2-quinazolinyl, or a 4-quinazolinyl group;
~ç.............. . . ..
, 8 :!,`', ~f',' ~ '!
~''' `' ' ~` ' ~' ., . , `, .

3L()~3~3 t those of the pyridazine type, such as a 2 p~ridazinyl, a 3-pyridazinyl, a 3-cinnolinyl or a 4-cinnolinyl group; those of the indolidine type, such as a l-indolidinyl, a 2-indolidinyl, a ;:
3-indolidinyl, a 5-indolidinyl, a 6-indolidinyl o.r a 7-indolidinyl group; those of the perimidine type, such as a 2-perimidinyl ~ :
group; those of the thiazole type, such as a 2-thiazolyl, a : 2-benzothiazolyl, a 3-isothiazolyl, a 4-isothiazolyl or a 5~
isothiazolyl group; those of the imidazole type, such as a 2- ~`
benzoimidazolyl group; those of the oxazole type, such as a 2-oxazole group; those of the 1,3,5-triazine type, such as a 1,3,5-triazinyl group; and those of the oxazine type such as a 2-oxazinyl group. These heterocyclic groups may be further substituted by any suitable substituent, for example, halogenatoms, alkyl groups, alkylcarbonyl cJroups, alkenyl groups, alkoxy groups, alkylsulfonyl yroups, aryl groups, aryloxy groups, . arylcarhonyl groups, arylsulfonyl groups, carboxyl groups, alkoxy-carbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, .
acylamide groups, ureido groups, sulfonamide groups, amino groups, : nitro groups, cyano groups, thiocyano groups, hydroxyl groups,acyl groups, aryloxycarbonyl groups, acylamino groups, alko~y-sulfonyl groups, aryloxysulfonyl groups and sulfoamino groups.
~nother embodiment of General Formula (I), includes those derivatives in which two residual groups RlCOÇ~ICONH- :
:' O=C~ ~=0 ;~ are bound to a heterocyclic group, to two heterocyclic groups : .
combined directly with each other or to two heterocyclic groups : combined via a bivalent group. In this case, the couplers may : be represented by the following general formula:
(R COCIHCONIl)2R
. ~ N
.. O=C~ \C=O
"-Z ' _ 9 _ , ,. . .
.. . .
.

~0~13~3 :-wherein R2 represents a divalent het~rocycli.e group.
General Formula (I) further includes bis-compounds sueh ~.
as those wherein two coupl~r groups RlCOCIHCONHR2 are bonded through Z, e.g~, see yellow-forming coupler ~43) described below.
In a preferxed embod~ment, the diacylamino group is selected from dicarboxylic aeid imido groups having the , following General Formulae (II) to ~XIII) `.... 10 ~III) O C/ \C O O= C/ \C O "
; R3 -\/C- C\- R5 R~ \R8 ~

' ~ " ,;
~IV) ~V) / N \ / N \ . .
O=C C=O O=C Ç=O ~' ' ' R10/ ~>C/ \R13 Rl -C~ /C\R18 1 \R12 R16 . 20 ~ (VI) ~VII) .. / N \ ~ \
o ~ ~ O=C C=O
Rlg c I R21 R22 f ~w ::

;' ! R2 0 R2 3 , ~ :
.' , i ~ . (VIII) I . (IX) ¦ ~.

~'" O=C/ \C=O O=C C-O '' ~ 30 R24- C~ / N_R26 R2 ~ \ o / \ R30 :~

,..................... R 5 ,,",,.,, -- 1 0 -- ' ,. :

3~3 (XI) N \ 0= C C-0 . ~.
O= C=O

l3~

'~', ~ XII) tXIII) ~
,"', ' I ,,`. :~, .
; 10 / N \ / N \ ::
O- C=O O=C C--O ' ::
~ R36 f l-R37 and R.3 ~ \ R
'. ' ' In the above General Formulae (II) to (XIII), R3, R , R , R6, R7, ~:: 8 9 10 11 12 13 1 R R R R R R
R , R , R , R , R , R , R
'h', ~ 22 23 R24 R25 R27 R28, R29, R30, R3 , R , R , R , R

and ~39 are each a monovalent substitutent such as a hydrogen .
:i. atom, a halogen atom such as fluorine, chlorine or bromine atom, -' an alkyl group such as a substituted or an unsubstituted alkyl ..
, 20 group having from 1 to about 32 carbon atomstpreferably having `;
from 1 to about 20 carbon atoms, an alkoxy group, an aryl group, an aryloxy group, a sulfo group, or a carboxyl group.
~: In formulae VI, VII, XI and XII R21, R26, R35, R36 and R37 -each represents a hydrogen atom, an alkyl group such as a substitu~
;: ted or unsubstituted alkyl group having from 1 to about 32 carbon ;~
. '.
atoms,preferably rom 1 to about 20 carbon atoms,or an aryl group. ~ :
: ~ ~ Moreover, yroups R3 and R5 in General Formula (II), R7 .~
and R in General Formula (III), R9 and Rll, and R 2 and R 3 in ~`
General Formula (IV), R15 and R16 and R16 and R17 in General Formula ~V), ~ 4 and ~25 in General Formula (VIII), and R31 and ~`
~''''` . . ', ~
~ .: , . .

? ~' .

1~413~3 1 R32 in General ~o~mula (X) ma~ be combined together to form a 5~ or 6~membered ring Which ma~ be either saturated or unsaturated.
Examples of such rings include a benzene rlng, a pyridine ring, a cyclohexane ring, a furan ring, a bic~cloheptane ring, a bicycloheptene ring and a cyclohexene ring.
W in General ~ormula (VII) represents an oxygen atom or a sulfur atom. ~ -Speci~ic examples of the residual group ~ : .
~ 10 / N
.: O=C C=O
. " Z-' .
; in th:e General Formula (I) include the followlng:
- ~'he two-e~uivalent couplers o the present invention represented by General Formula I are derivecl rom ~our-equivalent couplers represented by the following General Formula (I') and are linked at their coupling position by a single bond to a cyclic diacsrlamino group Rl _ C - C - C-- N \ (I'~

:. . , ;
wherein R and R are as defined in Formula I. The four-equivalent couplers represented by formula (I') are very well known in the photographic art. Numerous substituents have been provided on Rl and R2 in order to improve the characteristics of coupler per se and those of dyes formed from the couplers. I
Examples of these couplers can be found in the following ~ ~
~ references. "Mitteilungen aus den Forshungs-laboratorien der `
; ~ AGF~" b~ W. Pelz, Band 3, pages 1~2-126 (1961), U.S. Patent Nos. 3,409,439, 3,551,155, 3,551,156 and 3,649,276; British Patent ., , ,'"~; '~

' ' , ':' `:' ,: :

: . . . . . . . .

lV4~3~3 1 Nos. 1,961,156 and 1,286,411; Japanese Patent Publication Nos, 39-2,839 and 40-6,030; U.S. Patent Nos. 2,319,426, 2,331,326, .
2,350,138, 2,359,332, 2,376,679, 2,407,210, 2,46~,297, 2,472,g~3, 2,868,829, 2,875,057, 2,953l576, 3,056,67~, 3~0S6,675, 3,077,403, 3,341,331, 3,369,899, 3,393,041, 3,615,606, 3,619,190, 3,623,876, 3,645,742, 3,660,095, and 3,669,671; and Brltlsh Patent Nos.
805,505 and 1,187,860.
Since the two-equivalent couplers of formula ~I) provide the same azomethine dyes as those from the four-equivalent couplers of formula (I'), it can be expected that the Rl and R2 groups which provide dyes having desirable properties are also useful in ~ -the couplers of the present invention. Since the two-equivalent couplers of formula (I) are only modified by substituting the diacylamino group for one a-position hydrogen atom, it can also be expected that any of the Rl and R2 groups of formula (I') may be used as Rl and R2 in the couplers of the present invention.
It has been surprisingly found, however, that by the . .
substituting the diacylamino group for one a-position hydrogen , atom the remaining hydrogen atom at the a-position receives an electxonic effect and the coupler generally shows a decrease in its pKa value of about 3-4. Thus, in the couplers of the present ; invention Rl and R2 whether aryl ~Rl and R2) or heterocyclic (R2) , can be substituted with an electron-donating yroup which does not ~ reduce the coupling activity such as alkoxy group, amino group '~ or N-substituted amine group and maintain their sufficient coupling reactivity. It will be understood that Rl and R2 should not include a group adversely affecting to photographic emulsion such as a mercapto group, and sulfide group or a ' ~
peroxycarboxy group.
Typical specific examples of such dicarboxylic acid imide ~i ,.

" ., 3~3 residues are illustrated below: .

,: 11 . ~ ' ~C \ ."
:. N~ IH : ~
,;- . IJ ~

. C
CH - CH
-N 1 3 : I
CH
\C/ ~ ::

:~ 8 :. ~C\ ~ `

\C / 2 ~ ~ I

';,'. ~. :
R
; ~ 20 / CH C13H37 ;
-N ¦ ,:
\ / 2 ~::
~ ~ C~ ; ;
"~
, .; ~ , f" ~

~'~ ~ / \C/ ~ H
; ~ \ / \ / 2 ,,~ . ' l ',:

,;~; 30 ~- 1 4 ,~'' ' .',', . ~

~;i , .
,:. .
:. ...
,.:

L343 ~- ~
e ` ~
,, ~ C ' ' I
CH - Br . \C / . , '~'~

:: O
.; 11 ~ :
~, /C\
-N l C6H13 . \ f H2 ;.: :~
:' lC
O
,~ ~O .' ' :: / \c ~ 3 ~-N CH CH3 O
'"'' fl ,1 .~ /C\ /CH3 -N (1H C2H5 ' \,CI/ 2 ..
:: 2 0 ~
., . ~. " .

"' 1l ''`

~; -N H 2 ~,',, \~C~

.. :., :-N CH~

:, O

~, 3 0 , . .
~ 15 -- ~ ;

~ ~ .

,. . .
~ ";
a ., . -~ . .

~04~3f~3 `; ~
:.- 1 0 ~. ~.` .

-N CH (~?'~ - COOH
''''' ' ' `',, : ~

C CII - CH2~
I', 2 ~ :
,: ' ;~:' C--CH
,,;. 10 / /CH2 g CH2 C ---CH2~ /CH3 ~? n ~ 8 ;~
;.., . -N C -- CH -- C6H5 `. ~ :

;.; 20 ` b /~ - CH
; . --Cl -- CH

B ~ :
.,.~ . .

,;~ ` ~ .
.: 3 0 . . - 16 -,:,,: . .;

f;~ ~ .

.-.~ . .

~L~4~343 . ~
R
C ~- CH2\ /CH3 ~:
\ ICI r~ CH / 3 ,:
.. ..
Il ~C3~17 tn) -N/ =CH2 : 11 2 `

. .

/ C - CH2\ /C 3 -N ~C~ - CH

': ~C

., i , : ~ .

' 20 -N
"
:: s ~
',' q : ', CH 2 \ /CH 3 /C \
\ C - CH~ 2H5 ., ........................ Il b . . ~:

C - CH
~1: 30 . --N< CH2 1~ ~ C~ - bH
:; : - r :

r .~ 17 --,.. ,............................ . :
... .
... . .
. . .
~ .. ~ ~ .. . .. . .. . . . . . .. .. . . . .. . .

,(! ~H - C6H5 o .",~ ~, N~ ,~,C~I ~

C~l e ~C~I3 .`
' ' -N/ ~---- CH3 ~ ;
:; ' .'~

-N~ ~¢3_ .CE~3 f ~ ICl !
C~ ~
, ~ .

-N~
.~,~`,. . "~ .

-N ~Cl ~'" ' "' '' .
.,.,,` :
. r~
` ~- 1 8 r ~''` ' `~;

`! , ,` ~ :
.' '. :
''. ' ' :
: ' ',,' ' ~

R f~
-N ~

~ R ` :~:
-N~ ~ LOOH

<~2 ~ B2 ,',~ ~ ' ,.: .
~''`' ~ ` ~:

-N/ ~Cl ;~
: 20 U
;: R ~1 , 1 ,.. . .
~ - , 1:: ' <c~/C4Bg(t~

;- 30 :s :;
~.. '., - 19 - ' :
., ~: ~
:, . :

~=HCOCH3 -N/ ~3~NH50 , R ` ~
-N< ~NHCONH~ :

<I~NHCOCH~O~C5~111 (t N/ ~ 12H~ClSH31(n~
.' I ' ~
'; ' :.

~ ~NHCOCH CH ~<C4 9 ,-'.,'`' g ,,:
:': p ,'' -N < ~¢~
g `.... 30 ~:.
2 0 - ;

.: .

:
~ `

:: . . . . :, : . . ,. . . , , . ., . : : ` -3L04~3~3 ~ ~

. \C~ H3 .: .

-N< ~f CI~3 ~ ~ 8 ~; ~
o ~c ~ .

i, 8 ~:
R ~C f El ,. 1~

, 11 ~: <C~J

CI
~^ o ~ -- ., ~:~ 8 N2 j: R :

o . i 3 0 ~"" ' ' :

~;~i.,t,: .
~': ' ' ' ' .
~ .
~ .
, ~, , , ~ ~ : ,: ., . :` . . : : :

~43L343 :

~--NH ~ ~ NH\ , \C----C - CN3 -N~ H~C

C~13 `

~, e 2 1~ - NH /~
-N~ ¦ -N. f ~C - CH2 ~ -- C -- CH3 Il <CH ~e -` ' ` ' /C - NH /C - NH
i ~ ` \C ~ CH - C3H7 (n) ~C - C - CH3 ~ C - N - CH 3 : -N` ¦ :
lCI I CH3 ~ :~

~C2H5 ~

, .
, O

: ~ 30 ''' ' , ~,, ", :
,: , ~04~343 : ~

C ~ NH
~ ~N C~0 - ~C - C~ :~
/ 2 5 ` ~' C H

The process of forming yellow images according to this ; lnventlon may be divided into two modes, one where the couplers are present in the photographic emulsion la~ers of a photographic light-sensitive material and one where the couplers are present in color developers. In the former mode, the couplers are usually incorporated in silver halide photographic emulsion layers during the manufacture of the color photographic light-sensitive materials, and in the latter mode couplers are usually dissolved in color developers and they dlffuse in to the silver halide photographic emulsion layers of color photographic light-sensitive materials during development processing.
When the couplers are present in an emulsion layer, each ; coupler must be fixed in a specific emulsion layer, In other words, such a coupler must have a diffusion resistance since otherwise the coupler diffuses into other silver halide emulsion layers of the photographic light-sensitive material and causes a ::. .
~; coupling reaction in emulsion layers which have different spectral ,, .
sensitivities than the emulsion layer in which the coupler was originally present, and thus greatl~ reduce the color reproducirlg aculty of the light-sensitive material. ~;
In order to provide diffusion resisting property to a coupler, a hydrophobic group having 8-32 carbon atoms is ~; introduced in the molecule of the coupler. Such a group is usualIy called a "ballast or ballasting group". The ballast group combines with the skeleton structure of the coupler directly _ 23 ~
,, , .:

~LO~ 3 1 or through an amino bond, an ether bond, a thioether bond, a carbonamido bond, a sulfonamide bond, an urea bond, an ester bond, an imide bond, a carbonyl bond or a sulfonyl bond, in any one of R , R2 or Z. ~
Any known ballast groups can be used in the yellow-forming ~ -couplers of this invention. Typical examp:Les of such ballast groups are given below:
(i) Alkyl groups and alkenyl groups, such as / C2H5 -C12H2sr -C16H33 17 .. ~ also FIAT Final Report No, 934.

~ ii) Alkoxyalkyl groups, for example as described in the specification of Japanese Patent Publication No. 27,563/1964.
~, Typical examples thereof are:

2)3 ( 2)7CH3 and -(CH2)30CH2-CH-(CH2)8CH3 . : C 2H5 .:`
(iii) Alkylaryl groups such as -:
~ C~4Hg~t) :

; - CgHlg and ~ 4 9 , "
- (iV) Alkylaryloxyalkyl groups such as :

CH20 ~ CSHll(t) ~CH2 ~ sHll~sec) , sHll(t) C5Hl1(Sec) f~ ~ . . .
: . :
.~ 30 . . :~
. ,:
~,' . ' . ;,',. -:
. "''~

1~)4~343 -~ :

-CH2 ~ 5}lll(t) ~ l2 ~ C5Hll(t) CSHll(~eC) Hll~t) .
-(CH2)3 ~ SHll(t) 12 .~ ~1 (t~ l5H3l~n) -CH2 ~ SHll(t) and -CHO ~ 2 ll CH3-C-CH3 Hll~t) H2 C4H~(t) :~ See also British Patents 562,205 and 1,149,514 and U.S.
. Patents 2,589,004 and 2,908,573. Examples thereof are:

-CH2CH2N < 15 31 C4Hg .':
COC13~127 ' ~ .
. ' ~CE12CH2N~
3 7 ~:
and -CH2cH2NHcocH2cH2N < l3 27 ,......................... .
: (vi) Alkoxyaryl groups and ar~lox~ar~l groups such as :, , .

; ~ ~ OCl8H37(n) 30 .
~: ~ o ~ Cl2H25~n) . :

,. ~ . .' "

r . . ~ 25 ~ `

.. . .

1 See also Japanese Patent Publication No. 29,414/1968 and British Patent 969,921, (vii) Residues containing both a long chain aliphatic alkyl or alkenyl group, preferably with 12 to 32 carbon atoms, and - a water-solubilizlng carboxyl or sulfo group such as ~',`~ '. ' -cH-cH-cH-cl6H33 ~ CH COOH `-; and ~ CH C H ':
,~ SQ3H

coupler having a ballast group in the molecule is introduced into a silver halide photographic emulsion by dissolving it in an organic solvent and dispersing the solution in the ~ :
emulsion as fine particles in accordance with known methods. A
specific example of a method of dispersing the coupler into a photographic emulsion particularly suitable for the practice of this invention is explained in detail in the specification of ;-~
~:. 20 Japanese Patent Application No. 67,797/1969. The organic solvents . ~:
i~ used for dissolving the coupler include organic solvents which are only slightly soluble in water~ have a high boiling point ; (greater than 170C.) and which are present together with the !',' ', coupler in the photographic emulsion layers of a color photographic ~ :
~' light-sensitive material are substituted hydrocarbons such as `~
.~. . .~ . .
:. a~dodecyl naphthalene and chlorinated paraffins, carboxylic acid esters, carboxylic acid amides, phosphoric acid esters and ethers. ~
~j~ Specific examples of such materials are di-n-butylphthalate, di- ;
~ isooctyl azelate, di-n-butyl sebacate, tricresyl phosphate, tri-n-.' 30 hexyl phosphate, N,N-diethylcapr~lamide, butyl-m-pentadecylphenyl ~
~ ether and chlorinated paraffins such as chlorocosane. It is . ~ .
.: .
,~ - 26 -;; , .,i~, .
. .. '' ' .
, ~ '/ .. :

~0413~3 preferred to use, in addition to such a high boiling point solvent, up to 10~ by ~eight of the coupler~ most preferably no more than 5%, o~ a subsldiar~ solvent ~which can be removed during the manufacture of the light~sensitive material) to accelerate the dissolution of the coupler in the solvent. Examples of such subsidiary solvents axe prop~lene carbonate, eth~l acetate, ; butyl acetate, cyclohexanol, tetrahydrofuran, cyclohexanone, etc.
Also, it is preferred to use a surface active agent to finely disperse the oil-soluble coupler in a hydrophilic polymer 0 for the photographic emulsion. In particular, for such a purpose, ;~
an anionic surface active agent such as sodium cetylsulfate sodium p-dodecylbenzenesulfonate, sodium nonylnaphthalenesulfonate, ;
sodium di(2-ethylhexyl)-~-sulfosuccinate, and like surface active agents or a nonionic surface active agent such as sorbitan sesquioleic acid ester, sorbitan monolauric acid ester, etc., is suitable. The surface active agent~s) is usually used in an amount of 0.01~3~ by weight, based on the weight of coupler, more preferably 0.02~0.15%. It is also useful for dispersing the oil-soluble coupler to employ a homogenizer for emulsification, a ; colloid mill, an ultrasonic emulsifying means, etc.
A diffusion resistant or ballasted coup:Ler having a carboxylic acid group or a sulfonic acid group in combination with the ballast group in the molecule is soluble in a n~utral or weakly alkaline aqueous solution, i.e., at a hydroxyl ion concentration of 10 6 to 10 1 mole/liter, e~uivalent to a pH of 8~13. By adding the a~ueous solution of a coupler to a silver halide emulsion, the coupler can be incorporated in the photo-graphic emulsion. It is believed that the coupler becomes diffusion resistan-t by ~orming a micelle in a h~drophilic polymer.

A coupler having no such a ballast group, that is to say .; ' .
. ~ .

' - ' ~ .

. - .. , , . . , ~ . .

. " :

104~3~3 1 a coupler of the above t~pe of incorporated ln a color developer, is used in a color developer together with an aromatic primary amine color developin~ agent.
: Typical examples oE compounds among the yellow-forming couplers represented b~ the general formula I are shown below:
(1) ' , ~: OCH3 COCHCONH~lHCOOEIO~c5Hll ( / N \ C2H5 C ~ll(t) , >=< .
,," \~ ~';

~2) Cl ,. .
H3CO ~ COfHCONH
/ N \ HCOCHO ~ C5Hll(t) :~
OC CO I ~=/

; ' ' OCH

(3) ~ COCEICONH ~ ;~

. /C5~111(t) / OC CO ;~ ;
(t)HllCs ~ ~

:: . . .
. .:, , .
. 30 .... .
` ~' ~ .
';' " , ,':
. . .
.. . .

1(~4~343 Cl `

H3CO~ COCHCONH~ C~l (t) OC~ CO CONH (CH2) 3~ 5 ll (t) 1: ,~ ' '`

b ~ ,~
~''t, ~"` ' (5) . ...
. 1 0 Cl H3CO~ COICHCONH~ C~ t) -: OC~o --hHCOfHO~ C5Hll (t) 2H5 ::
~.' .
i ( 6 ) ;
, ~ Cl ,:
~OCHCONH~

OC~ ~CO l4H2 9 ;'. /
~` ~ ~G , ,~ , :'s'~ (7) C2~I5

4~--OC CO . COOCH2CHC4Hg ~: 30 ~ `

~` ` . ... . ..

~: :

1~4~34~ :
(8) ;

~COCHCONH~

OC CO COOC~I2CHC4H9 (9) j-~COCHCONH~ ~ .i \--/ I \=~ -~ /N~ \CCl2 25 CH 3 OC~=~ O

'~' ~ ' '"': '.', ~ .
- '.
; :" .
.'; (10) , ~,.. ..
OCH
~0 l H(:ONH~

OC ~CO C14H29 ~;
.. \~ ~''.

', " ' ';~ (11) ~ .
~.
OCH3 - ~ .

.: ~OCI HCONH~\~ -.- ` 3 0~N~ ~ `
OC~CO C00C14H2g . ;~

.: , : ..
; . , .

~0~13~3 ~12) -- C~l .. D~COCHCONH~/ \~
\=/ ~N\ \=~
OC CO ~oocH2f~IcgHl7 '~' , ~ ~ 13 ~ ~

~.
:
(13) OCH3 ;~

~0 1 HCOIIH~
of lo Cl4H29 ~. H3C IC NH
1. CH3 . .
, , , ~
,~"
(14) ~ H3CO~OCI HCONH~/ ~) C~;l (t) NHCOCHO~_CSHll (t) ~ f f 12H5 ~ .
H3C--f NH
~; CH3 :
, ,. . ~ .
~'' ~. ..

( 15 ) ,,~, . .
: . C~ 1 :

t ~I3CO~COfHCONH~ (~
;,j. `~ 30 . C~N~fo HCO (CH2? 30~--CSHll (t) ::~.......... . H3C-- tC NH
; C4Hg (sec) ' ::
.i . -- 31 --''.:

1~)4~343 :
(16 ) C8H17 - ~
~COCHCONH~ ~ ~ ;
of co cooc8H17 (sec) H7C3 H NH

(17 ) ~ .

H3C~o lCHCoNH~
,' OC\ CO ;., ~}ICOCO~C5}~ t) ;~

(18 ) OCH
:, ~ 3 : :
H3Co4~CO ICHCONH~

5Hll(t)F' OC/ CO ~;02N(C2H5)2 (t)}lllC5~0f};C~

... ~ . . .
. . .
,~.;` . ~-.
,. . .

.. :.. ~ .
. . 3~
,~ - 32 ~
.,. ., ~ , ''' ' ' ..
:

. ~

`

,. 1 ~19 ) ~, OCH

H3Co4~COCHCONH~
11 ~t) ,~~ OC~ O --bo2N (C2~15) 2 (t)HllC5 y~fc H ;~

, ' ' ';' "

(20) Cl ~3CO~CONHCIICONH~ C~l(t) HCOCH20--~C 5 11 I,,J :, :

(21) Cl 20H3CO~OCI HCONH
: ~N
' OC CO t:ooCl2H25 `.

': ~,, 22) . Cl H C(~-COCHCON~ C~l (t) OC'~ ~CO HCO (CH2) 30~CSHll ~t) 3 0 ~13C ~l~3 : ' . , ., j,~:
., - :
.,. '"- "~:
~ 33 r .. . ..

~0~3~3 1 ~23 ~ 3 H3CO- ~ COCHCONH - ~ C ~ 1( ) OC ~ O HCOCH-O

,: H ;. `;
~. ~
'. `'' ` -, ' 10 (24) ;~

OfHCONH ~ Hll~t) CH3 o ~ O NCOfHO ~ CSHll(t) ' 3 ¢.~
;', ;~ (25) `~; COOH

H35C17~ COfHCONH
" OC CO COOH
,''''' ' ~< ''' .
.... ..
26) Cl H3CO ~ CO~HCONH ~

i',;`:' OC CO NHCOC~IClH=cHcl6H33 ;.~ ~
``` \ ~ H2COOH -:, ' ' ,.:~

~; ,. , ,, , ,:, 'V
,,, ~4~3~
t27) ~`
~03H `
H3 7C1 8~--CO~HCONH~ -OC~CO H3 ., .

. : .

~28) OCH ~.
~ 3 ~OCIHCONE

H33C16C ~ OC CO
:, H2COOH I ..

. CH3 ` ~ .

~ (29) . .
:,` ,. ..
:' . .
Cl '.'~

CN30~COCEICONN~
,~ 20 C/ \ O HCO tCH2) 30~C5Hll (t) . ~ ~C ~ "
,' ~ . '.

~30) ;;

C~
CH30~CO~HCONE~ 1 2~5 OC CO NHCOCNO~
;; ~< C15H31 ( ) ;

.,. , ~.`

'" ~;

:' ' ~

104~43 ~: ~
( 3 1 ) O~CH3 ~CO ~CHCONH~ :
~N~ ~: :
'' OC CO ,~.:

., '.'~' .;;~, '.

~32) :` OCH3 ~COCHCON~) .'. I \=/ `` :~
'' OC~ ~O ' ''' . ` . .
` (33) ^

. C l 33C~3co~co~
. OC CO 2 . . \ / .:
", ' )~( . ''':
. . ~d ,~ , (34) :-~: C~l ~,0 I HCONH~

~) ,, ,. . ..

" ' . _ 36 ' , ?~-~

~ ~L04~343 35) H3CO- ~ OfHCONH

~: OC ~CO HCOCH3 ~-CH3 `. ~:~
: ~ .
`: . ;. ~
`:. (36) OOEICONH~
~' C 3 ol C10 C12H25 ~: H3C- C N -CH3 ~, CH3 .
,~. ,,~. .
~, . " . .
, (37) :; .

OCHCONH ~ :

oc co C14H29 \C/ ..':.
:~ 20 2~ C2H5 ~

' '. ! :: , : ~38) ```

C~
,~ H3CO ~ COCHCONH ~ .
C ~; OC COHCOfHO ~ C5Hll(t) H3C - I - N_CH32 5 ~5Hll~t) _ 37 _ ~

:i.;, : :
:.,~, "~
i~,,; ::

.,~, . . ...

~,,,",,,, ,, ,,,,,,,,,, ,,,, ",",.. ... .. ..... .

~0~3~3 ~:(3g) C~

3 ~COCHCONH~

\C/ C2H5 ~5Hll(t) '~
. (40) ,, 3 ~ COCHCONH--QC
OC Co OOH

~ ~ .
\N C C H (n) (41) . :
' ~COI HCONH~S03K ~ ~
OC CO , 2 0 ~~C H
: 12 25 ',.
(42) ,~CH 3 COI HCoNH~3NHco~Hco~cH3 :: OC CO c~3 OC CO
,. . I I l I~ - :
.. --`Cl8H37 ' `C18H37 .- .
.: , 3 ~
:~ -- 38 -.`~,~, .
.

.~ :
~','' ...
.. . . . . .

(43) ~CC12~25 COI HCONH--y~ ) . . .
o / \ o C/~
':, \ / . ~, ~' :-~. ~ ;`

f.'' \ / C 1 . .
~ ~OCHCOElEI~
OOC H

;. ~, `
., . j . .
4 4 ) , :, ,' :: ~

~COCHCOEIH~NHCOCHCO~

:1 OC C1 0 OC ÇO ,'~
H3C C ~H H3C--C NH
14H9 ~iso) C4H ~iso) `~?

(45) C~Hll(t) A' ~ (t)H11~5~0CHCONH --NEfCOCHCO~COfHCONH~HCOCHO~
:~ ~ ~ ~N~ H
`C5Hll (t) 1 OC CO O IC Cl O :

~; . 3 0 CH 3 ~s~

.,, 1~13~3 1 The yellow-formlng couplers o~ this invention can be ; ~;
prepared by reacting a 4~equivalent coupler in which one of the hydrogen atoms of the active methylene group is substituted for ... .
with a halogen atom, preferably a bromine atom, and an imide.
compound, the imide compounds are those which correspond to the 0=Ç Ç=0 moiet~ heretofore defined in General Formula (I) and "Z' :.
the free imide or the salt from thereof can be used, in the presence of an inorganic basic material, preferably potassium hydroxide or sodium hydroxide or an organic basic material, preferably, triethylamine or 1,4 diazabicyclo 2,2 octane in an ; organic solvent. In the above reactionl a salt of the correspond-ing imide compound with an inorganic or organic basic material can also be used in place of the free imide compound, In the ;~ latter case, the inorganic or organic basic material used in the above reaction may not be necessary. ;
The amount of basic material is not overly critical, but best results are obtained when about 1 - about 2 moles of basic material are used per one mole of imide compound. Greater and lesser amounts of basic material can be used with success, however.
The solvent which can be used in the reaction includes an amide solvent such as dimethylformamide, dimethylacetamide, ~ hexamethylphosphoramide etc., having a dielectric content of ,~ more than 30, N-methyl-2-pyrolidone and tetramethylurea and an oxide solvent such as dimethylsulfoxide. The exact amount of solvent used can be varied within a wide range and is not overly critical so long as sufficient solvent is present to permit the .
; reaction to smoothly pxoceed. ExCellent results are obtained using 3~ about 5 ~ about 20 weight parts of solvent per 1 weight part of ~ imidè, however.
.,.
4~

.; ' ' , ' , ~04~34~
1 ~he reaction ~roceeds at a low temperature and at a high rate to pro~ide the objective coupler of high purity and at high yields using such solvents.
On the other handl when the synthesis of 2-equivalent ~ ;
couplers is conducted by refluxing with heating and employing ;~
acetonitrile as a solvent, as is described in Japan Patent Publication No. 26133/72 and U.S. Patent No. 3,408,194, is employed to prepare a coupler of this invention, the desired --coupler cannot be adequately obtained. This is because side 10 products are formed in great excess and it is very hard to :

separate and purify the desired product. The main side product is a dimer of the coupler bonded at a coupling position.
The imide compound is desirably used in a molar e~cess based on the coupler, preferabl~ in a 1.5 to 3 times molar excess.
The reaction can proceed within a broad temperature range, preferably at from 0C to 80C.
The amide solvent and the sulfoxide solvent can be used alone or as mixtures of two or more thereof. In order to control the reaction rate, the solvent can be diluted with commonl; 20 employed solvents including alcohols such as methanol, ethanol and isopropanol; halogenated hydrocarbons such as chloroform and `
.. . .
, methylchloroform; hydrocarbons such as ligroin and hexane, aromatic hydrocarbons such as benzene, toluene and xylene;

~;i acetonitrole and the like. `

The preparation of the yellow-forming couplers is . . .
illustrated in further detail by the following examples.

~ynthesis example 1 Synthesis of 2'-chloro-5'-[a-(2,4-di-t-amylphenoxy)butyl-~ amino~4-methoxy-a-phthalimido-benzoylacetanilide (Coupler 2~:

- A mixture of 70 g of 2'-chloro-5'-[~-~2,4-di-5-t-:.-.
?~
.
~,,," ~
,: .
. .
: .. , . . . - :

~ ~4~3~3 amylphenoxy)-buty]amido]-4-methoxy-a-bromobenzoylacetanilide and 55 5 g of phthalimide potassium ~as stirred in 500 ml of dimethyl-sulfoxide for 4 hours at xoom temperature. The reaction product was poured in 2 liters of water and extracted with one liter of ethyl acetate. The ethyl acetate layer formed was recovered, washed with a diluted hydrochloric acid solution ~5~ HCl~, washed with water and then dried over Glauber's salt. By distilling ethyl acetate off under reduced pressure (15~30 mm Hg) and recrystallizing the product from a solvent mixture of ethyl acetate and hexane tl:4), 55 g o the Coupler 2 having a melting point of 155-157C was obtained.
Synthesis example 2 Synthesis of 2'-chloro-5'-tetradecyloxycarbonyl-~-phthalimido-benzoylacetanilide (Coupler 6~:
A mixture of 16.3 g of 2'-chloro-5'-tetradecyloxycarbonyl-chloro-benzoylacetanilide and 18.5 g of phthalimide potassium was stirred in 300 ml of dimethylformamide for 3 hours at room temperature. The reaction product thus obtained was treated as in Synthesis example 1. Upon recrystallizing the product from methanol, 12 g of Coupler 6 having a melting point of 81 82C.
was obtained.
Synthesis example 3 Synthesis of 3-[a-(2,4-di-t-amylphenoxy)butylamido]-5'-N,N-diethylsulfamyl-4r2'-dimethoxy-a-phthalimido-benzoylacetanilide (Coupler 18):
.
A mixture of 16.5 g of 3-[a-(2,4-di-t-amylphenoxy)butyl-amido3-5'-N,N-diethylsulfamyl-4,2'-dimethoxy-~-bromo-benzoylacet-anilide and 11 g of phthalimide was stirred in 250 ml of dimethyl-".
- 30 formamide for 3 hours at room temperature. The reaction product was treated as in Synthesis example 1 and the product obtained , . . .
~ - - 42 -.~. . :
.~.~: .. .
}~...... ' ~
,, .

3~3 `~ ~ :
1 was recr~stallized fxom a solvent mixture of ethanol and ligroin (1:1), Upon recr~stallizing the product from acetonitrile, 11.5 g ~ ~
of the Coupler 18 having a melting point o~ 197-200C. was ~ ;
obtained.
Synthesis _ ample 4 Synthesis of 2'-chloro-5'-[a-(2,4-di-t-aminophenoxy~butyl-amido]-4-methoxy-a-succinimido-benzoylacetanilide tCoupler 5): ~
A mixture of 50 g of 2'-chloro-5'-~a-(2,4-di-t-amylphenoxy)- ;
butylamido]-4-methoxy-a-bromobenzoyl-acetanilide and 30 g of - succinimide potassium was stirred in 300 ml of dimethylformamide for 3 hours at room temperature. The reaction product was ~
treated as in Synthesis example 1. Upon recrystalliziny the ; ;;
. .
product from a mixture of ethyl acetate and hexane (4:4), 36 g :
of the Coupler 5 having a melting point of 138-139C. was obtained.
Synthesis example 5 Synthesis of 2'-chloro-5'-~a-~2,4-di-t-amylphenoxy)butyl-amido]-4-methoxy-a-(5,5-dimethyl-3-hydantoinyl)-benzoylacetanilide (Coupler 14):

A mixture of 35 g of 2'-chloro-5'-[a-~2,4-di-t-amylphenoxy)~
butylamido]-4-methoxy-a-bromo-acetanilide and 25 g of the potassium ~! ~ "
salt of 5,5-dimethylhydantoin was stirred in 250 ml. of dimethyl-,:
formamide for 3 hours at room temperature. The reaction product thus obtained was treated as in Synthesis example l. Upon recrystallizing the product from ethanol, 18 g of the Coupler 14 ~-having a melting point of 122-125C. was obtained.
Synthesis example 6 . ~, - . .Synthesis of 2'-chloro-4-methoxy-5-nitro-a-phthalimido-benzoylacetanilide ~Coupler 33): ;

- 30 A mixture of 30 g of 2'-chloro-4-methox~-5-nitro-a~bromo-.: . :
,,., ~.
~ 43 -.,~ ..

, ..................................................................... ... .
., ~

, .
,"'~ ' ~04; L3~3 1 benzoylacetanilide and 39 g of phthalimide pota8sium was stirred in 400 ml of dimethylformamlde Xor 3 hours at room temperature.
The reaction product was treated as ln S~nthesis example 1. Upon recrystallizing the product from methyl cellosolve, 14 g of the Coupler 33 having a melting polnt of 203-205C. was obtained.
Synthesis example 7 .
Synthesis of 5'-amino-2'-chloro-4-methoxy-~-phthalimido-benzoylacetanilide (Coupler 34):
10 g of 2'-chloro-4-methoxy-5-nitro~a-phthalimidobenzoyl-: 10 .~:
acetanilide prepared in Synthesis example 6 was added to 100 mlof 90% acetic acid. The mixture was heated on a steam bath and then 5 g of reduced iron was slowly added to the mixture with :: ~
stirring. The reaction product was filtered, the filtrate ~.~as poured in one lltex of water, and the crystals thus formed were recovered by filtration~ washed with water and recrystallized from ethanol to provide 4 g of the Coupler 34 having a melting point of 105-107C.
Synthesis example 8 Synthesis of 2'-chloro-5'-a-2,4-di-t-amylphenoxy butyl-amido-4-methoxy-a-phthalimido-benzoylacetanilide (Coupler 2):
The synthesis of example 1 was repeated except for using 400 ml of dimethylacetamide in place of 500 ml of dimethyl-`~ formamide with stirring for 30 minutes. The reaction mixture was treated as in Synthesis example 1 to obtain 60 g of the ~oupler 2 having a melting point of from 155 to 157C.
Synthesis example 9 '~ Synthesis o~ 2'-chloro-5'-~-~2,4-di-t-amylphenoxy)butyl-~;~ amldo-4-methoxy-2(5.5-dimethyl-3-hydantoinyl)-benzoylacetanilide (Coupler 22):
~ 44 ~
.

1.
", ~04~iL343 1 32 g of 2'-chloro-5'-~-(2,4-di-t-amylphenoxy)butylamido-4-methoxy-a-bromoacetanilide was dissolved into 200 ml of hexamethylphosphoramide~ To this solution was added a solution having dissolved therein 25 g of 5.5 dimethyldantoin and 12 g of potassium hydroxide in 30 ml of methanol, and the combined -~
` solution stirred for one hour at room temperature. The reaction mixture was processed in a manner similar to Synthesis example 1 except for recrystallizing from acetonitrile to obtain 26 g of - Coupler 22 having a melting point of from 142 to 143C.
S~nthesis example 10 ,., ~" ~
Synthesis example 8 was repeated except for usinq a mixed solvent of 200 ml of dimethylformamide and 100 ml of acetonitrile to obtain 23 g of coupler 22 having a melting point of ~rom 142 to 143C.
S~nthesis example 11 ' :' .'. , Synthesis of 2'-chloro-4'-dodecyloxycarbonyl-2-methyl-a~
phthal-imido-benzoylacetanilide (Coupler 9~
29 g of 2'-chloro-4'-dodecyloxycarbonyl-2-methyl-a-bromo-benzoylacetanilide, 29 g of phthalimide and 20 g of triethylaminewere stirred for 3 hours at room temperature in 200 ml of dimethylformamide. The reaction mixture was processed in a manner similar to Synthesis example 1 except for using ligroin for recrystalli~ation to obtain 20 g of Coupler 9 having a melting point of from 100 to 101C.
Having thus described several synthesis examples in accordance with the present invention, it is appropriate to turn to a more detailed description of photographic elements as are forme~ in accordance with the present invention.
The silver halide photographic emulsion used in this , .
~ invention is a dispersion of any photosensitive silver halide as ~
: ~ , ' - ~5 ~
.

'; :
- . . :. . - . . : ~ ". ~ - ..

.. 34;~ ::
is used in the art such as silvex chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chlorolodobromide in a hydrophillc polymer as colloidal grains. The grain size of the silver halide used in the present invention is not critical, and can vary over the range of material a~l are currently usea in the art. The average graln size is prefe~ably about 0.05~5~, more preferably 0.1-2~.
The photographic emulsion can be prepared b~ various methods, for example, as described in "Chimie Photographique"
(2nd. ed. 1957, Paris) by P. Glafkide's. Direct-positive emulsions of the internal-image type as described in "The Theory of the Photographic Process" ~3rd. ed. 1966, N.Y.) by Mees and ~ames can also be used in the present invention.
Typical examples of hydrophilic polymers which can be used to form the silver halide photographic emulsion are proteins such as gelatin, high molecular weight non-electrolytes such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acrylamide, etc., high molecular weight amphoteric electrolytes such as the polyacrylamide treated by a Hoffman's decomposition reaction (see A. M. Schiller and T. J. Suen; Ind. Eng. Chem., Vol. 48, p. 2132-2137 ~1956)) and a copolymer of acrylic acid and N-vinylimidazole. Other useful hydrophilic polymers include polyvinyl acrylamides such as polyacrylamide cellulose derivatives, polyvinyl alcohols or hydrolyzed polyvinyl acetates as described in U.S. Patent 2,286,215, hydrolyzed cellulose esters such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in U.S. Patent 2,327,808, water-soluble ehtanolamine r ' cellulose acetates as described in U.S, Patent 2,322,085, and ~ .
polyacrylamides having a combined acrylamide content of 30-60 and a specific viscosity of 0.25-1.5 on an imidized polyacrylamide ..

~,. ..

~: ' .. .. .. . . . ; ..

~0~:~3~3 ~
of like acrylamide content and viscosi y as described in U.S.
Patent 2,541,474, zein as described in U.S. Patent 2,563,791, vinyl alcohol pol~rmers containing urethane carbo~ylic acid ;~
groups of the type described in U.S. Patent 2,768,154, vinyl alcohol pol~mers containing cyano-acetyl groups, such as the vinyl-alcohol-vinyl cyano acetate copolymers described in U.S.
Patent 2,808,331 and polymeric materials which result from polymerizin~ a protein or a saturated acylated protein with a :
monomer having a vinyl group as described in U.S. Patent /"~ 10 2,8521382.
The silver halide photographic emulsion in this invention may further contain various additives which are ordinarily added to conventional silver halide color photographic emulsions, such ~ -as sensitizers, stabilizers, hardening agents, surface active agents, and the like.
For example, sensitizers such as ta) speed-increasing compounds such as those described in U,S, Patent Nos. 2,271,623, 2,288,226, 2,334,864 and 2,708,162 and (b) compounds increasing the light~sensitivity of the silver halide as disclosed in British Patent 1,221,875, German Patent 2,1;37,559 and Japanese Patent ~pplication Nos. 19,034/70 and 30,023/71; stabilizers such : .
; as benzotriazole, 5-nitrobenæimidazole, 1-phenyl-5-mercapto-.~. . tetrazole and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene; hardeners such as those described in U.S. Patent Nos. 3,325,287 and 3,362,827 and Japan~se Patents 257,564 and 309,487; surface : ::
~ active agents such as those described in U.S. Patent Nos.

.:. 3,441,413 and British Patents, 1,164,0g5 and 1,012,495; ana ` anti-oxidants such as those described in U.S. Patent Nos.

2,360,290 and 2,403,721.
:-. 30 . `:
,.'! The above described silver halide photo~xaphic e~ulsion :~:
:
,, . ' ::
~ ~ ~7 ~
','' , ~ ' .

~04~3~3 1 containing the yellow-forming coupler of ~his invention in one embodiment of this invention ma~ be applied to various photo-graphic supports. Typical examples of such supports are cellulose acetate films, polystyrene films, polyester films, polycarbonate films, papers, papers coated with a polyalkylene such as polyethylene and glass plates.
The aromatic primary amine developing agent used in this invention includes a compound having a primary amino group at ;

the aromatic ring thereof and has the ability to develop exposed silver halide and also a precursor capable of forming such a compound. In the practice of this invention, o-aminophenol, p-aminophenol, N,N-di-substituted-o-phenylenediamine, and in . . .
particular N,N-p-phenylenediamine, are most o~ten used.
Specific examples of such primary aromatic amine developing agents are 4-amino~3-dimethylamino-N,N-diethylaniline, 4-amino-3-ethoxy-N,N-diethylaniline, 4-amino-3,5-dimethyl-N,N-diethyl-aniline, 4-amino-3-methyl-N-ethyl-N-(~-hydroxyethyl)aniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-3-methyl-N-ethyl-N-(~-methylsulfonamidoethyl)aniline, 4-amino-3-(~-methylsulfonamido-ethyl)-N,N-diethylaniline, 4-amino-N-ethyl-N-(~-hydroxyethyl)-aniline, 4-amino-N,N-diethylaniline and 4-amino-N-ethyl-N-~ -sulfobutylaniline. Additional examples of useful materials are set out in Mees-~ames: "The 'rheory of ~he Photographic Process" (3rd ed. 1966, N.Y.) in Table 134 on pages 294-295, specifically those compounds marked "++" in Table 134. The : . ~
developing agent concentration is not critical and is usually about 0.5 - 50 g/liter, with from 1 g - 20 g/liter being most , i preferred.
The color developer used in this invention ma~ contain, in addition to tlle aforesaid developing agent, various additives ,, ~ _ ~8 -r'' .

, '. A . . ~ . . . .

1 as are usually used ln color developers. For instance, alkali metal sulfites, carhonates, iodides~ bromides, benzyl alcohol, etc.
The coupler used in this invention has the feature that one hydrogen atom on the a-position carbon atom of the a-(aromatic acyl)acetamide has been substituted by an N-cyclic carboimide ~ ~;
group. That is to say, a nitrogen atom activated by two carbonyl ;~
groups is bonded to the a-posi~ion carbon atom of the acylacetamide.
It is considered that the oxidation product of the aromatic primary amine developing agent reacts with said a-carboimido-acylacetamide compound to split the bond between the imido nitrogen atom and the a-position carbon atom and to form an azomethine dye and an imido ion.
The coupler used in this invention has the following valuable features.
The a-imidoacylacetamide type coupler of this invention ; is a 2-equivalent coupler, that is, it requires only two equivalents of silver halide as an oxidizing agent to form one molecule of dye. Thus, as compared with a 4-equivalent acylacetamide type coupler which is conventionally widely used, the amount of silver halide required is reduced one half with ;~
the use of the couplers of this invention, and thus the proportion of silver halide contained in the silver halide photographic emulsion layers of photographic light-sensitive materials can be reduced. Accordingly, not only can the production cost of the pAotographic light-sensitive materials be reduced, but in addition light scattering due to silver halide grains in the -~
:~ j photographic emulsion layer can be reduced and thus the sharp- ;

ness of the image formed can be improved. Furthermore, in the -~ 30 ; case o~ this invention the thickness of the silver halide emulsion , - , ' '~
. :' .'-" ' '~
;~ 1 -, ,. ~ . . ., , . , . . :

~0~34~ ~
1 layer contalning the coupler can be reduced due to the reduced proportion of silver halide, and thus the time re~uired for development can also be reduced, The imide t~pe coupler used in this invention has a high coupling reactivity with the oxidation product of the aromatic primary amino developing agent, and thus the oxidation product :- of the developing agent formed at color development is quickly . removed and the development of the silver halide emulsion is promoted. Thus, the formation of the dye image of this invention is conducted in a short period of time. Also, due to the high react.ivity of the coupler of this invention, sufficient coupling or coloring is obtained even if the amount of solvent, in particular the non-volatile solvent for dispersing the oil soluble coupler in a silver halide emulsion, is greatly reduced.
By reducing the amount of solvent remaining in the silver halide . photographic emulsion layers of a light-sensitive material, the ~,.
mechanical strength of the emulsion layers can be increased.
In the case of employing the acylacetanilide type coupler substituted by an imide group in accordance with the present invention, the dye-forming step is finished in a color developing . :, bath and thus in subsequent processings, the use of a bleaching bath containing a strong oxidizing agent such as potassium ferricyanide or potassium bichromate is not necessary, and the developed light~sensitive materia]. can be processed in a blixing bath containing a weak oxidizing agent such as the ferric chelate complex of ethylenediaminetetraacetic acid, which results in making it possible to shorten the total color development processing time and to reduce the problem of water pollution due to waste processing liquid such as ferricyanide wastes. On ;~ 30 the o~her hand, in the case of using many conventional acylacet-..
-- S O
.,~j ~., , ... .
., , . . .
~ .

.. , : , , . , . . . ~ "

1~3gL~3~3 ~ ~
1 amide type couplers wherein the coupling reaction point has notbeen substituted, the coupllng reaction ls not ~inlshed in the color developing bath, i.e., a considexable poxtion of the product of the coupling reaction remains as the state of colorless leuco form and to completel~ color the colorless leuco form, a strong oxidizing agent is required.
When the d~e image produced from the imide-substituted - acylacetamide type coupler used in this invention is preserved under severe conditions for a long period of time, it shows a low tendency to fade.
The silver image b~-produced in the step of forming the dye image according to the present invention is readily oxidized in the bleaching bath or the blixing bath, and the reduced silver can be completely removed during processing in a short period o tlme. Accordingly, a sharp, clear yellow d~e imaqe ~ !
without stains due to residual silver can be obtained in accordance with this invention.
The imide-substituted acylacetamide type coupler used ; in this invention can be produced at high yields by using starting materials as are easily available in the industry.
The amount of the coupler used in this invention is , .
influenced by the kind of photographic light-sensitive material in which it is to be used and the type of the developing process, but a range of from 0.02 to 1.0 mol of coupler per mol of - silver halide in the silver ha~ide emulsion is particularly -~
useful and from 0.1 to 0.5 mol of coupler per mole of silver halide is most preerred. If the amount is less than the lower limit, a large amount of silver halide is required to give the coloring extinction coefficient required by the light-sensltive ~ material, which results in increasing the light scattering of the silver halide emulsion layer and reducing the sharpness .,. :
:' . - 5 1 -~';' ' ' .,:

.. ~ .. ,, . , . . . , ., , . ~ . . . . . .

~a~4~343 1 of the image. That is, an increase in the amount of silver in a silver halide emulsion is accompanied with an increase in the thickness of the emulsion layer and a reduction in the speed of the developing processing of the emulsion layer. On the other hand, if the amount of the coupler is lar~er than the upper limit, the conversion of the coupler into dye becomes insufficient, thereby reducing the efficiency of utilizing the coupler. Thus, the use of such a large amount of coupler reduces the economic advantages as well as increases the thickness of the silver 1 halide emulsion layer. Thus, outside the addition range of the coupler set out above, the merits of this invention cannot be sufficiently obtained.
In the embodiment where the coupler is in the developer, the coupler should be present in the developing bath at a level of from 0.1 to 10, preferably from 0.5 to 5 g/liter of developer.
As described in the foregoing, when amounts outside the range ~; described above are used, the advantages and objects according to the present invention cannot be sufficiently obtained.
j <~ The couplers represented by general formula I may be ; used individually or may be used as combinations theraof.
Furthermore, the coupler of general formula I may be used together with other couplers.
The invention will now be further illustrated by the following examples which comprise preferred embodiments of the invention.

": :, A solution prepared by heating a mixture of 28.8 g of ~; Coupler (2), i.e. a-4t-methoxybenzoyl-a-phthalimido-2-chloro-~; 30 5-~a-(2",4"-di-t-amylphenoxy)-butylamido]-acetanilide, 30 ml of ~ di-n but~l phthalate and 50 ml of cyclohexanone, to 70C was ,. . :

~ - S2 -! ' ~,........................................................................ .

~(~4~3~3 1 added to 300 ml of an a~ueous solution containing 30 g of gelatin and 2.0 g of sodium dodec~lbenze-nesulfonate followed by stirring. Then, the mixture was pre heated to 45C and passed through a colloid mill five times, whereby the coupler was finely dispersed in the solvent.
: The total amount of the emulsified dispersion of the coupler was added to 1.0 kg of a photographic emulsion containing 54 g of silver iodobromide (molar ratio ]C:Bx - 3:97) and 60 g of gelatin and after further adding to 30 ml of 3~ acetone solution of trieth~lene phosphamide to the mixture as a hardening .. :.
agent, the pH of the mixture was adjusted to 6Ø Then, the :: :
silver halide emulsion thus prepared was applied to a triacetyl cellulose film in a dry thickness of 7.0 microns to provide ~ :
~: a photographic light-sensitive material, which was called Sample A. The coupler content in Sample A was 1.96 x 10 3 . mol/m2.
A comparisoni sample of a photographic light-sensitive ~. material was prepared following the same procedure as in the : production of Sample A using 23.5 g of a-4'-methoxybenzoyl-2- :;
: 20 chloro-5-[a-(2",4"-di-t-amylphenoxy)butylamido}-acetanilide ;
; ~Coupler a) in place of Coupler 2 and the comparison sample was `:
called Sample B.
.~ Each of the photographic light-sensitive materials was . subjected to a step exposure for sensitometry under a ~
graduated optical wedge with light of 50 CMS for 1/20" (see ~:
: Russell Campbell: "Photographic Theory for the Motion Picture ~ .
, ~; ~ Cameraman" (lst ed., 1970, N. ~.) and then subjected to the : ~
.:. . . .
following processings: : :

.`. 1, Color development ~.0C15 minutes 2~ Water washing 18C 1 " ;:
. . .
: ~ 53 ~ ~ ~
.: .
. ', .
,:
.....
~,; , :.., r 4~L3~;3 1 3~ ~lrst fixing 20C 4 minutes 4. Water washing 18C 3 "

5. Bleachinq 20~C 5 "

6, ~ater washing 18C 3

7. Second fixing 20C 3 "
: 8. Water washing 18C 15 ;. The composition of the color developer used in the above color development was as ~ollows:
Color developer A
Water 1000 ml : 4-Amino-3~methyl-N,N-diethylaniline hydrochloride 2.5 g ` Anhydrous sodium sulfite 3.0 g ; Sodium carbonate ~mono-hydrate) 47.0 g Potassium bromide 2.0 g The fixing solution used in the above processiny was ~ an acid aqueous solution containing sodium thiosulfate and ~:
; sodium sulfite and the bleaching solution used above was a neutral solution containing potassium ferricyanide and potassium ~:
. 20 bromide:
Fixing solution Sodium thiosulfate (anhydrous) 153.0 g ,. Sodium sul~ite (anhydrous)15.0 g '.: Glacial acetic acid . 13.5 ml Boric acid 7.5 g Potassium alum 15.0 g ~-. ~ ~
~ Water to make 1000 ml j~ pH 4.25 ~ 0.25 at 25C ;~
. Bleaching solution ` 30 Potassium ferricyanide 50.0 g . , ~ 54 -,;" ~

,; . .
.,, , ~ :.

~04~3~3 ~
1 Potassium bromide 20.0 g Water to make 1000 ml pH 6~5-7,0 at 25C

. After processing, the optical densit~ to blue light ; was measured for Sample ~ and Sample B, the results of which . are shown in Table 1, The color image of both samples was a sharp yellow image with the absorption maximum at 454 milli-microns.
. .
Table 1 : Sample Coupler Fog Sensikivity* GammaMaximum ~(relative) density : A (2) 0.18 100 2,S7 3.24 B ~a) 0,12 96 1,63 2.51 t*): exposure amount re~ulred to obtain a density ~.10 above fog.

Then, the "maximum density to blue light" for Sample A
:
~: and Sample B, obtained when the samples were processed while ~ changing the processing time for the color development was : measured r the results of which are shown in Table 2, : 20 Table 2 . Sample Coupler 5 Development time ~m2inutes) ~ ;

A ~2) 2,66 3,25 3.24 3,27 :;
. B ~a) 1.69 2.32 2.51 2.53 .. These results show that the imide group-substitu~ed '!-' coupler used in the process of this invention could gave higher :; . ., sensitivity, gradation, and coupling density than unsubstituted coupler (a) used in the comparison sample, and further in the ~: :
case of using the coupler of this invention sufflcient color was obtained in a shorter period of time, which reduces the . ` total processing time, This clearl~ shows that the imide;
,:
~: - 55 -~: .
.~,.,, ~.

,',,. ' ~04~343 :~
1 substituted coupler has a higher coupling reactivity than an unsubstituted one.
To further clarify the lmproved coupling reactivity of the coupler of this invention, the following expe iment was conducted.
A silver bromide emulsion ]a~er containing a mixture of (2) or ~a) and a cyan-forming coupler ~b), 4,6-dichloro-S-methyl-2-[a-(2',4'-di-tert-amylphenoxy)-acetamido]phenol was : . .
developed in color developer A at 21C for 14 mins, where the two couplers react competitively with the oxidized developing agent to give a mixture of yellow and cyan dyes. Then, by analysing .. . .
the formation ratio of the yellow dye to c~an dye, the relative value of the reaction rate constant of the coupling reaction for D, the yellow-forrning coupler based on the cyan-forming coupler (b) ~ was obtained.
,~; The coupling reactivity of a coupler is determined as a relative value by color developing a silver halide emulsion `~
containing two kinds of couplers A and B of which give different colors which can be clearly separated from each other, and measuring the amount of each dye in the dye imaye thus formed.
; If coupler A shows a color density DA, the max. value of which iS tDA) max., and coupler B shows a color density DB ~ the max.
value of which is tDB~ max., respectively, the ratio RA/RB o the reactivities of the both couplers is shown by the following ~ equation:
.?' ' ' ' r B ~ax i.: ~ . . ~;
.~,, _ ~ _ .. . .
~ ~B
$ -;
;~ 30 logtl- - (D ) ~ ~ 56 -.,.,. .

:, . .

1()4~343 ~
1 That is to say, the coupling re~ctivity ratio RA~RB is ~ :
obtained from the gradient of the line obtained log(l-DA/(DA)max?
vs lg(l~Dg/(Ds)maX~) . As a result, the relatlve rate constant of the imide-substitu-ted coupler (2) o~ thi~ invention was 6.6, while that of the conventional unsubstituted coupler (a) was 1.1. The results show that the coupling reactivity of the imide type ;~
coupler used in this invention was 6 times higher than that of the conventionally known unsubstituted coupler.

; Sample A and Sample B prepared in Example 1 were sub-jected to step exposure for sensitometry under a graduated optical wedge light of 100 CMS for 1/~0'l and processed as follows:
1. Color development 24C 8 minutes 2. Stopping 24C 2 "
3. Blixing 24C 6 ~ 4. Water washing 24C 5 1l , : The color developer used in the above color development '~; 20 processings was the same as in Example 1, and the composi.tions . :
o~ the other processing solutions were as follows;
.~ Stopping solution .
Water 1000 ml :
Anhydrous sodium sulfite 5.0 g ~.
; Glacial acetic acid 15.0 ml. .
. Blixing solution .. - Water 1000 ml Ammonium thiosulfate 105.0 g - Sodium sulfite 80 g ~ 30 . E. D. T. A. ~disodium salt) 35.0 g .~ Ferric chloride (hexahydrate) 25.D g . Potassium thiocyanate 10,0 g - 57 ~
... . .

:
.... . .

~04~ 3 1 After processing, the optical densit~ to blue light was measured for each sample. Then, each sample was immersed in a 1.5% aqueous solution of potassium ferricyanide for 2 minutes at 24C,, washed with water for 10 minutes, and dried, Thereafter, the optical density to blue light was meas~ured again, the results of which are shown in Table 3.
Table 3 SampleCouplerPost treatment by ~erricyanide solution Be~ore After i'" 10 (i) (ii) ~iii) (i)' ~ii) (iii) A(2) 0.19 2.52 3.28 0.19 2.53 3.30 B(a) 0.12 1.24 1.96 0.13 1.6- 2.55 (i): fog; (ii): gamma; ~iii): maximum density.

As is shown in Table 3, it is clear that in the case of using the imide-substituted coupler ~2) of this invention, the formation of the color image was finished in the steps of color development and blixing, while in case of using convention~l unsubstituted coupler (a), the formation of the color image in those steps was only about 3/4 completed and the remaining reaction product was in a colorless state. In order to completely convert the colorless reaction product into dye, processing r' with a strong oxidizing agent was required. Thus, the results show that using the novel imide-substituted yellow-forming s; coupler of this invention, the number o~ color development ,. ~ .
processings can be reduced. -i;~, . . _-- , .
r~ ' A mixture of 63.7 g of Coupler (19), a-~4'-methoxy-3'--[a-(2",4"-di-t-amylphenoxy)butylamido]~ benzoyl-a-succinimido-:.... . . . .

~ 30 2-methoxy-5~(N,N-diethylsul~amo~ acetanilide, 65 ml o~ tri~n-'I'' ~, ~: .
,- ~ 58 -,:

i .
:. ~
, ~ "i :
. , ~ .

~ i3~3 1 hexyl phosphate, 100 ml of ethyl acetate, and 3,2 g of sodium dinonylnaphthalenesulfonate was heated on a steam bath to prepare a solution. After adding the solution to 700 ml of an aqueous solution of 50 g of gelatin, the mixture was stirred and then further stirred vigorously in a high speed agitator whereby the coupler was finely dispersed in the solvent. ~
` The total amount of the thus obtained emulsified ~ -dispersion was added to 1,5 kg of a photographic emulsion containing 0.30 mol of silver chlarobromide (molar ratio of lOCl:Br=30:70) and 100 g of gelatin, and after adding further 15 ml of a 4~ aqueous solution of 1-hydroxy-3,5-dichloro-S-triazine as a hardening agent ana adjusting the pH of the mixture to : . .
6,5, the mixture was applied to a baryta-coated paper (which was coated on both surfaces with polyethylene) to a dry thicknsss of 3.0 microns to provide a photographic light-sensitive material, which was designated Sample C. The content of the coupler in Sample C was 1.03 x 10 3 mol/m .
For the sake of comparison, an emulsified dispersion of a comparison coupler was prepared following the same procedure as was used in preparing Sample C using 56.4 g of ~- ~4'-methoxy~

3'-ia-(2~',4''-di-t-amylphenox~)butylamido]~-benzoyl-2-methOxy-5 (N,N-diethylsulamoyl)~acetanilide (Coupler C) in place of the Coupler (19).
The total amount of the emulsified dispersion thus prepared was added to 3.0 kg of a photographic emulsion containing 0~60 mol of silver chlorobromide and 200 g of gelatin, and after adding to the dispersion 25 ml of a 4% aqueous solution of the sodium salt of l-h~droxy-3,5-dichloro~S-triazine and adjust-ing the pH of the mixture to 6,5, the mixture was applied to a baryta-coated paper as was used to ~orm Sample C in a dry :..: ,:
~ - 59 _ .:.
... .
.. . .
.:
:

~4:~3~3 1 thickness of 4.0 microns to provide a photographic light-sensitive material, which was designated Sample D. The content of the coupler ln Sample D was 1,01 x 10 mol/m .
The silver halide emulsions used for preparing these samples were pr.epared b~ dividing the same silver chlorobromide :
emulsion into two portions and diluting each part with an aqueous -~
: gelatin solution if necessary. The content of coupler was the same in each emulsion but the content of silver was different.
Each of the samples was sub~ected to a stepwise exposure for sensitometry as in Example 2 and then processed as in Example 1 except that the same was developed in a developer B
having the following composition for 12 minutes at 2~C.
Color developer B -.
Water 1000 ml Be~zyl alcohol 12.0 g Sodium hexametaphosphate 2.0 g Anhydrous sodium sulfite 2.0 g Sodium carbonate (monohydrate) 27.5 g ~i`

. Hydroxylamine sulfate 2.5 g ,:: 2~
: 4~Amino-3~meth~1-N-ethyl~N
(~-methanesulfoneamidoethyl)-aniline sesquisulfate (monohydrate) 4,0 g .
: After processing, the reflection optical density of . each sample thus processed to blue li.ght was measured, the results of which are shown in Table 4. .

Table 4 i:~

: Sample Coupler AgX/coupler Fog Sensitivity Gamma Maximum . .. mol.ratio. ....... .. ~relative) . . density __ . . . . .. . _ . , .
C (19) ~ 0.15 100 . 2.06 1.63 D (C) 8 Ø10 87 1.28 1.47 .

`: ' :
. . .
.. ;:
,, ' ' ,' :.

i~)41~43 :
1 From Table 4, it is clear that coupler (19) of this invention showed a higher degree of coloring than unsubstituted coupler (C) havlng a corresponding structure, even in the case of using less sllver halide whereby and the thlckness of the ~; ;
emulsion layer could be reduced.

A solution prepared by heating a mixture of 5 x 10 3 mol of each carbonimide group~substituted coupler mentioned above, 4.5 ml of di-n-butyl phthalate, 8 ml of cyclohexanone, and ; 0.2 g of bis(2-ethylhexyl)-a-sulfosuccinate (sodium salt) on a hot plate was added to 60 ml of an aqueous solution containing 5 g of gelatin and the mixture was stirred vigorously in a `-~
homoblender to finely disperse the coupler. `
The total amount o the coupler dispersion thus obtained was added to 150 g o a fine grain silver hallde emulsion containing 3.8 g of silver bromide and 13 g of gelatin and the ~' mixture was applied to a cellulose triacetate film in a dry ~ thickness of 7 microns to provide a photographic light-sensitive ; film By exposing each of the photographic lightesensitive films and developing it as in Example 1, a yellow image was obtained. The spectral absorption characteristics o~ each yellow dye image was measurecl by means o a spectrophotometer and the absorption maximum values as are shown in the following table were obtained.

i~, . . . , :
- Table 5 ~
i. .:
Coupler Absorption Coupler Absorption maximum (~u) maximum (~

~::,, . . , --(1) 446 tl5) 455 (2) 454 ~1~) 454 .~,,,,~ . ~
. .
:
... .
. .
.. ,, :
;; , .. . . .

104i39L3 ~ ~
1 Coupler Absorption Coupler Absorption .maximum .(~) ...... . .~aximum .(~) 13) 447 (17) 453 , ~, (4) 454 ~18) 45~ . ~
(5) 455 (lg) 453 -~ -` ~6) 457 (20) 455 -~
~7) 451 t21) 450

(8) 45~ ~22) 454 (g) ~55 (23) 446 `
, . , lO (10) 448 ~24) 448 49 (26) 455 `
~12) 457 (28) ~50 13) 448 ~29) 454 ~1~) 454 ~30) 454 As is clear rom the results shown in Table 5, the couplers o~ this invention have absorption maximum in the range of 440-460 microns,.and thus have spectral absorption characteristics suitable for color reproduction by a subtractive . color process. . .
:~ 2~ ~ EXAMPLE 5 .. ..
A solution prepared by heating a mixture of 26.5 g of Coupler ~13) ~-benzoyl-~-(5',5'-dimethyl-3'-hydantoinyl)-2-methoxy-t-tetradecylcarboxyacetanilide, 25 ml of di-n-butyl ~ ;
; phthalatej and 55 ml of ethyl acetate to 60C was added with stirring to 400 ml of an aqueous solution containing 5.0 g of ~ ;~
.~ ~ sodium di-~2-ethylhexyl)-a-sulfosuccinate and 36 g of gelatin .. and the emulsion obtained was passed twice through a milk -. ~ homogenizer, whereby the coupler was ~inely emulsified in the `~
~ ` sol~ent.
.`. 30 ~:. - 62 ~.:
'''. ~:
~;~' , ''J' ~ ~, !: `

:

~aO~L~L3~3 1 The total amount of the emulslfied dispersion thus prepared was added to 700 g of a photographic emulsion containing 22.6 g of silver iodide (2 mol% iodide) and 50 g o gelatin, and after addlng to the mixture 20 ml of a 3~ acetone solution of tri-ethylene phosphamide as a hardening agellt and adjusting the pH of the mixture to 6.5, the mixture was applied to a baryta- .
coated paper (having on both surfaces polyethylene layers) in : a dry thickness of 3.5 microns.
A gelatin solution was further applied to the silver halide emulsion layer thus formed in a dry thickness of 1.0 micron as a second layer and further a green-sensitive silver halide emulsion containing a magenta-forming coupler ~d) having :~
the following formula was applied thereto in a dry thickness of 3.5 microns: C2H5 : 1 ~ HCOCHO ~ C5Hll(t) 3 ~ \ 1l_cH2 5~ t) .~ 20 A gelatin solution containing 2-(2'-benzotriazolyl)-4,6 dibutylphenol sufficient to provide a coating concentration of 1.2 g/m2 was applied to the green-sensitive emulsion layer in a thickness of 2.5 microns as a fourth layer. Then, a red-:..
sensitive silver halide emulsion layer containing cyan-forming coupler (e) having the following formula was applied thereto as a fifth layer in a dry thickness of 4.0 microns:
OH
NH~cH2)3ocl2H25 , ................................................................. .
Cl ': - 63 -: ' .

, . .

10~ 3 Finally r a gelatin solution was applied to the red-sensitive emulsion layer ln a dry thickness of 0.5 micron as the uppermost layer to provide a color photographic paper.
The green- and red-sensitive emulsion layers had the following concentrations of components, respectively:
. _ _.
- Components Ag Br-Cl Coupler Gelatin 50:50 mole Green-., .
: sensitive Coverage 9.0xlO 329.0xlO 4 2 3.1 g/m ~, lO mole/m mole/m ... .
!' :
, Components ~ Ag Br-Cl CouplerGelatin , 50:50 mole X Red-~, sensitive ~" Coverage 5.5xlO 32 l.lxlO 3 23.6 g/m . . .mole/m mole/m ~
:.' ' ., A color negative was optically printed on the color ~; photographic paper prepared as above and the color paper was processed in the color developer B and in the blixing solution as in Example 2. The color print thus obtained showed an excellent color reproducing faculty providing a clear color.
~ ~ The yellow dye image had the absorption maximum at 443 milli-s~, microns.
"s EX~MPLE 6 .~. , .
A solution prepared by heating a mixture of ~4.2 g of Coupler (9), i.e., 2'-chloro-5'-dodecyloxycarbonyl~2-methyl-benzoylacetanilider S0 ml of ethyl acetate and 25 ml of di-n-bUtyl phthalate, to 50C was added to 250 ml of an aqueous ~: solution containing 25 g of gelatin and 1.25 g of sodium dodecyl~
benæenesulfonate followed by vigorous stirring by means of a homo-blender to ~inel~ disperse the coupler.

~ 64 -.... , .
`s'..
i.' . :
,.,:.:: ~ :
, .. .
.,~, . .

-~L0~3.3~3 1 The total amount of the emulsified dispersion of the coupler was added to S00 g of a photographic emulsion containing 28 g of silver bromide and 35 g of gelatin and, after urther adding 15 ml of a 2~ aqueous solution of 1-h~droxy-3,5-dichloro-s-triazine sodium salt to the mixture as a hardening agent, the pH of themixture was ad~usted to 6.5. Then, the silver halide emulsion thus prepared was applied to a triacetyl cellulose film in a dry thickness of 5.0 ~u to provide a photographic light-sensitive material, which was called Samp:Le E, The coupler content and the silver amount in Sample E were 1.74 x 10 3 mol/m2 and 0.76 g/m2, respectively.
In order to prepare a comparison sample, a solution prepared by heating a mixture of 18.8 g of 2'-chloro-S'-dodec~loxycarbonyl-2-methylbenzoylacetanilide (coupler b, illustrated below) in place of Coupler ~9), 35 ml of ethyl acetate and 20 ml of di-n-butyl phthalate, to 50C was added to ; 200 ml of an aqueous solution containing 20 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate followed by vi~orous stirring b~ means of a homo-blender as above to finely disperse the coupler.

: .
. . .
~OOC H
OC~l2CONH ~ ~Coupler b) The total amount of the emulsified dispersion of Coupler b was added to 1 kg of the same s.ilver bromide emulsion as above and, a~ter further adding 20 ml of the same solution of the hardening agent as above, the pH was ad~usted tv 6.5.
Then, the silver halide emulsion thus prepared ~as applied to a ' .- .

:,.
',' . .

.

104~343 triacetyl cellulose base in a dr~ thlckness of 6,0 ~ to provide a photograph.ic light,sensit~ve material, Which was called Sample F. The coupler content and the silver amount in Sample F were 1,77 x 10 3 mol/m2 and 1.54 g/m , respectively.
Each of the photographic light~sensitive materials was sub~,ected to a step exposure for sensitometr~ and then processed as described in Example 1.
After the processings, the optical density to blue light was measured for Sample E and Sample F, the results of which are shown in Table 6, Table 6 Capabilit~ of color formation Sample Coupler Molecular Fog Sensitivity y Maximum ratio of ~relative todensity Sam~,le E=100) _ _ ,. , E ~g) 4/1 Q.25 100 2.563.04 F ~b) 8/1 0.22 98 2.172.93 Then, the maximwn density for Sample E and Sample F to blue light obtained when the samples were processed while , "
changing the processing time for the color development as gi.ven ~; in Example 1 was measured, the results of which are shown in ;,., ~
.. Table 7.

;~ Table 7 Change in capability of color formation , with development time Sample Coupler Molar ratio Development time (minutes) ~; of A~X/Coupler 5 10 15 20 -E, (9) 4/1 2.80 3.03 3.04 3.00 ~; F (b) 8/1 2.41 2.82 2.93 2.98 . . ~, ~- These results show that the imide group-substituted ~ 3~ Coupler (9) used in the process of the invention could give high ; sensitivity, gradation, and coupling density through the silver - 66 - ;

": . . .

.

1 amount had been reduced to 1/2 of that o~ the unsubstituted Coupler (b), and further that su~icient colo~ Was obtained in a shorter period of tlme, whlch reduces the total processing time, ': ;
To stud~ the equivalence pro~erty so as to claxify the fact that the silver amount necessar~ to ~orm 1 mol of dye from improved Coupler (9) showing a good color~forming property is 1/2 of the amount necessary in unsubstituted Coupler (b) having a corresponding structure, the followin~ experiment was conducted.
Each of Sample E and Sample F was subjected to a step ;
exposure, then subjected to the processings up to processing ; step 4 described in Example 1. Then, the amount of silver deposited in the samples containing the color-forming dye and the silver deposit was determined by means of a fluorescent X-ra~ Quantometer. The samples were then subjected to processing steps 5 - 8 as described in Example 1. Thereafter, the formed dye was extracted from the thus processed samples with a mixed solvent of N,N-dimethylformamide and water ~85:15 by volume) and analyzed. The results thus obtained are shown in Figure 1.
In Figure 1, the molar ratio of amount of silver ,....................................................................... .
deposited amount of colored dye in the case of the unsubstituted Coupler (b) is shown to be 5.5 - 6.0, whereas that in the case ... .
of Coupler t9) in accordance with the invention is shown to be 2,5 - 2.8, which clearly shows that the molar ratio with the ,. .
coupler in accordance with the present invention is less than 1/2 of that as achieved with the unsubstituted 4-quivalent coupler.
EXAMPL~ 7 A solution prepared by heating a mixture of 56.0 g of Coupler (14), i.e., 5'-[a-~2,4-di-tert~amylphenoxy)-butyl-~,; .
, ' . . : . - - - .
,:; . . , . . - . ~, .

~04~3~3 amido]-2'-chloro-4~methox~ (5,5-dlmeth~1~3~hydantoinyl)-benzoylacetanilide r 100 ml o~ eth~l acetate and 50 ml of di-n-butyl phthalatc, to 50C was added to 500 ml of an a~ueous solution containing 50 g of gelatin and 2 5 ~ of sodium dodecyl-benzenesulfonate followed by stirring. Then, the mixture was ;~
passed through a pre-heated colloid mill five times, whereby :, the coupler was finely dispersed in the solvent.
The total amount of the emulsified dispersion of the coupler was added to 1 kg of a photographic emulsion containing 10 56 g of silver bromide and 70 g of gelatin and, after further adding 30 ml of a 2~ aqueous solution of l~hydroxy-3,5~dichloro-s-triazine sodium salt as a hardening agent, the pH of the mixture was adjusted to 6.5. Then, the silver halide emulsion thus prepared was applied to a triacetyl cellulose film in a dry thickness o~ 5.0 y to provide a photographic light-sensitive ~ }naterial, which was called Sample G. The coupler content and the silver amount in Sample G were 1.70 x 1~ 3 mol/m2 and .
0.75 g/m2, respectively.
A comparison sample of a photographic light-sensitive ~ material was prepared following the same procedure as in the production of Sample G using 61.5 g of Coupler ~c~, i.e., 5'-[a-(2,4-di~tert-amylphenoxy)butyl-amido]-2'-chloro-4-methoxy-a-benzofulfimido-benzoylacetanilide, a compound containing a coupli.ng off group represented by the formula -N 2 z , which is analogous to that of the present invention and described .:
:;
~: in West German Patent OLS No. 2,057,941, in place of Coupler (14).

The resulting comparison sample was called Sample H. ~:

'; . .

',;' ' ` ' , ':

39,~3 ;~
,, , ~ .

NHCOlHO ~ C5Hll(t) OCHCONH ~ ~5~11(t) O-C ~ 2 ~Coupler C) ""'~

: .
The coupler content and the silver amount in Sample H

were 1.73 x 10 3 mol~m2 and 0.77 g/m2, respectively.
In order to prepare another photographic light-sensitive materlal comparison sample, an emulsified dispersion was prepared :.. , ~ .
following the same procedure as in the production of Sample G
using 46.6 g of Coupler (a), i.e., 5'-[a-(2,4-di-tert-amylphenoxy)-butyl-amido~-2'-chloro-4-methoxy-benzoylacetanilide, which was illustrated in Example 1. The total amount of the emulsified dispersion was added to 2 kg of the same emulsion as was used in ;~
the production of 5ample G and, after adding 40 ml of the hardener, the resulting coating solution was coated in a dr~ thickness of 6~0 jU to provide a photographic light-sensitive material, which was called Sample I.
The coupler content and the silver amount in Sample I
were 1,77 x 10 3 mol/m2 and 1.59 g/m2, respectively.
Each of the thus prepared samples was subjected to a step exposure for sensitometry and then subjected to the same pro-cessing as described in Sample 3.
.. ~, . .
~- After processing, the optical density to blue light was measured for these samples, the results of which are shown in Table 8 ~i! 30 ,...: -, ;,.,. :
..,:...
~,:" -.

~,.` ' : ' ' ,." , ~V~L~343 1 Table 8 ~ . ~ .
Capabillt~ of color formation Sample Coupler Molar ratio Fog Sensitivity ~ ~aximum - of AgX/Coupler ~lr.e.l.~tiv.e.) .. density .. . ~ .
: G (14) 4~1 0,05 100 2.30 2,87 H ~c) 4/1 0,06 99 1.86 2.61 ::
I (a) 8/1 0,03 96 1.79 2.49 .
~ urthermore, samples obtained by processing the same samples in the same manner as above were exposed to a 1.5 W
0 xernon arc lamp (l~O,OOO lx) for 80 hours while placing in ~ront of the samples a W filter interrupting light of wave-lengths shorter.than 400 m~ to compare the light-fastness of the formed color images. The results obtained are shown in Table 9.

Table 9 ~:
Light~fastness of colored images.
.:. Sample Coupler Initial dens.ity before exposure ,, 0 5 1.0 2.0 . G (14) 28 25 20 H (c) 76 69 61 - ::

I ta) 44 41 34 ;:

The numerical values in Table 9 shows the percentages :
o the reduction in the density to blue light based on the initial density to blue light.
In addition, with similarly processed samples the formed - ~ images were stored for 20 days under conditions of constant temperature ~60C) and constant humidity (70~ RH), and then the . ~astness was compared. The results obtained are shown in - Table 10. ~

' 30 ~ :

~ 70 .' .
: .
. , .
. . . ....... . ... .... .

13~L3 1 Table 10 Fastness of formed i~ages under high humidity and high temperature Sample Coupler Irltic~
0.~ 1,0 2.0 G tl4) 5 3 3 H (c) 48 45 37 , I (a) 5 5 5 ; , :
The numerical values in Table 10 show the percentages -1~ of the reduction in the density to blue light based on the ; initial density to blue light. ;
From the results set forth in Tables 8, 9 and 10, it -~ is clear that Coupler ~14) used in the present invention exhibited greater color density as compared with that in the unsubstituted Coupler ~a) having a corresponding structure and Coupler (c) having an analogous coupling-o~f group represented by the formula -N \ Z
CO~
described in West German Patent OLS No. 2,057,941 and, in addition, that the coupling-off group exerted a great influence on the fastness of the formed image to light and heat-humidity, whereby Coupler (1~) of the present invention showed excellent , .:
~ ~ fastness.
~, . . .
Furthermore, in order to study the equivalence property, ~ -each of Samples G, H and I was processed in the same manner as :
`;~ described in Example 7. Then, the amount of silver deposited and the amount of colored dye were determined. The results thus obtained are shown in Table 2, In Figure 2, the molar ratios of amount of sllver ~, ~' ' ~ .
~, :
~'' .
.... ~... . , . ... ., . .. ..... ~ .

:~4~ 343 1 deposited amount of colored dye in the case of unsubstituted Coupler ~a) and in the case of Coupler (c) having an analogous coupling-off group represented b~ the formula ~N ~ 2 ~z .: CO_ _, descrlbed in West German Patent OLS No. 2,057,941 are 6.0 - 6.5 and 2.8 - 3.3, respectively, whereas that in the case of Coupler (14) in accordance with the invention is 2.2 - 2.5, which clearly shows that the molar ratio ~i.e., equivalence property) ~-; of the coupler of the present invention is less than 1/2 that of , .
the unsubstituted 4-equivalent coupler ~a) and less than in the case of Coupler (c).
., . ;
` While the invention has been described in detail and t" . with reference to specific embodiments thereof, it will be apparent to one skilled ln the art that various changes and ~` modifications can be made therein without departing from the spirit and scope thereof. -~
.: r: .

``
,,, ' ~ , .., :,'"
': , ' ~"
,., :".' :.. . ......................................................................... .
.,. ~ , - ., .... .
,.: . , . :

~ 72 -i . ~
!: ' ' ' :
~ ,~
, ;::
... .
.` : ' . .
'.`'' ~

Claims (30)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A photographic light-sensitive element comprising a support having coated thereon at least one silver halide emulsion layer containing a yellow dye forming coupler having the following general formula:

wherein R1 is an aryl group, R2 is an aryl group or an hetero-cyclic group, and Z is the non-metallic atom or atoms necessary to form, with the moiety in said general formula, a 4-membered, a 5-membered or a 6-membered ring.

2. A photographic light-sensitive element comprising a support and having coated thereon at least one silver halide emulsion layer containing a yellow dye forming coupler having the following general formula:
Claim 2 continued . . .
wherein R1 is an aryl group, R2 is an aryl group or an heterocyclic group, and Z is the non-metallic atom or atoms necessary to form, with the moiety in said general formula, a 4-membered, a 5-membered or a 6-membered ring, and wherein at least one of R1, R2 or Z contains as a substituent a hydrophobic group of from about 8 to about 32 carbon atoms.

3. The photographic light-sensitive element as claimed in

claim 2 wherein said coupler has the general formula:

wherein R1 represents (1) a phenyl group; (2) a substituted phenyl group, wherein said substituents are one or more members from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarboxyl groups, alkylsulfonyl groups, arylsulfonyl groups, carbonyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; or (3) a condensed aromatic ring having the formula wherein A represents the atoms necessary to form an aromatic condensed ring system;
R2 represents (1) a phenyl group; (2) a substituted phenyl group, wherein said substituents are one or more members from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, arylcarbamyl groups, alkylcarbonyl groups, alkylsulfonyl groups,

Claim 3 continued . . .
arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; (3) a heterocyclic group bound to said - group in the general formula through a carbon atom in said heterocyclic group which is part of the conjugated electron system and selected from the group consisting of the thiophenes, furans, pyrans, chromenes, pyrroles, pyridines, pyrazines, pyrimidines, pyridazines, indolidines, perimidines, thiazoles, imidazoles, oxazoles, 1, 3, 5-triazines and the oxazines;
and the substituted derivatives thereof, said substituents being selected from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups,aryl groups, aryloxy groups, alkyl-carbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; (4) a condensed aromatic ring having the formula wherein A represents the atoms necessary to form an aromatic condensed ring system.

4. The photographic light-sensitive element as claimed in claim 2 wherein said Z is selected from the group consisting of .

Claim 4 continued ...

, , , , , , , , and , wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33, R34, R38 and R39 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group, or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

5. The photographic light-sensitive element as claimed in claim 2 wherein R1 is a group represented by the formula:
and R2 is a group represented by the formula:

wherein X is a halogen atom, an alkoxy group, an aryloxy group, or a tertiary amino group, and Y1, Y2 and Y3, which may be the same or different, are each selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups and cyano groups, Y4 and Y8, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups and alkoxy groups, Y5, Y6, and Y7, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups and acylamino groups; and Z is selected from the group consisting of , , ,

Claim 5 continued ...

, , , and , wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33, R34, R38 and R39 are each a hydroyen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R 17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 5 membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

6. A photographic light-sensitive element comprising a support coated thereon at least one silver halide emulsion layer containing a yellow dye forming coupler having the general formula:

Claim 6 continued...
wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group and Z is selected from the group consisting of , , , , , and , wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33, R34, R38 and R39 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 4-membered, 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

7. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula:

wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group and Z represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a four-, five- or six-membered ring.

8. A method for forming aye images comprising exposing a light-sensitive element having on a support a photographic emulsion layer containing an .alpha.-diacylamino substituted yellow dye forming coupler of the general formula wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group and Z represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula,

Claim 8 continued ...
a four-, five- or six-membered ring, and wherein at least one of R1, R2 or Z contains as a substituent a hydrophobic group of from about 8 to about 32 carbon atoms, and processing the exposed element with an aqueous alkaline solution containing an aromatic primary amino developing agent.

9. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula wherein R1 represents (1) a phenyl group; (2) a substituted phenyl group, wherein said substituents are one or more members from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; or (3) a condensed aromatic ring having the formula wherein A represents the atoms necessary to form an aromatic condensed ring system; R2 represents (1) a phenyl group; (2) a substituted phenyl group, wherein said substituents are one or

Claim 9 continued....
more members from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, arylcarbonyl groups, alkylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; (3) a heterocyclic group bound to said group in the general formula through a carbon atom in said heterocyclic group which is part of the conjugated electron system and selected from the group consisting of the thiophenes furans, pyrans, chromenes, pyrroles, pyridines, pyrazines, pyrimidines, pyridazines, indolidines, perimidines, thiazoles, imidazoles, oxazoles, 1,3,5-triazines and the oxazines; and the substituted derivatives thereof, said substituents being selected from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; (4) a condensed aromatic ring having the formula wherein A represents the atoms necessary to form an aromatic condensed ring system, and Z represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a four-, five- or six- membered ring.

10. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group, and Z is selected from the group consisting of , , , , , and , wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30 R31, R32, R33, R34, R38 and R39 are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and

Claim 10 continued ....
R8, R9, and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 4-membered, 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom, and wherein at least one of R1 or R2 contains as a substi-tuent a hydrophobic group of from about 8 to about 32 carbon atoms.

11. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula wherein Z is selected from the group consisting of , , , ,

Claim 11 continued....

, and , wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33, R34, R38 and R39 are each a hydrogen atom, a halogen, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 4-membered, 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom, X is a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, and Y1, Y2 and Y3 , which may be the same or different, are each selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups and cyano groups, Y4 and Y8, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups and alkoxy groups, Y5, Y6, and Y7, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups and acylamino groups.

12. method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group and Z is selected from the group consisting of , , , , , and , wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R,22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33, R34, R35 and R39 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group,

Claim 12 continued...

an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 4-membered, 5-membered or 6-membered ring, wherein R21, R26, R35 and R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

13. A photographic light-sensitive element comprising a support having coated thereon at least one silver halide emulsion layer containing a yellow dye forming coupler having the general formula:

wherein R1 is an aryl group, R2 is an aryl group or a heter-cyclic group, and Z is the non-metallic atom or atoms necessary to form, with the moiety in said general formula, a 5-membered or a 6-membered ring.

14. A photographic light-sensitive element comprising a support and having coated thereon at least one silver halide emulsion layer containing a yellow dye forming coupler having the following general formula:

Claim 14 continued ...
wherein R1 is an aryl group, R2 is an aryl group or an heterocyclic group, and Z is the non-metallic atom or atoms necessary to form, with the moiety in said general formula, a 5-membered or a 6-membered ring, and wherein at least one of R1, R2 or Z
contains as a substituent a hydrophobic group of from about 8 to about 32 carbon atoms.

15. The photographic light-sensitive element as claimed in

claim 14 wherein said coupler has the general formula:

wherein R1 represents (1) a phenyl group; (2) a substituted phenyl group, wherein said substituents are one or more members from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl group, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; or (3) a condensed aromatic ring having the formula wherein A represents the atoms necessary to form an aromatic condensed ring system; R2 represents (1) a phenyl group; (2) a substituted phenyl group, wherein said substituents are one or more members from the group consisting of halogen atoms, alkyl

Claim 15 continued....
groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, arylcarbonyl groups, alkylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acyl-amino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; (3) a heterocyclic group bound to said group in the general formula through a carbon atom in said heterocyclic group which is part of the conjugated electron system and selected from the group consisting of the thiophenes, furans, pyrans, chromenes, pyrroles, pyridines, pyrazines, pyrimidines, pyrida-zines, indolidines, perimidines, thiazoles, imidazoles, oxazoles, 1, 3, 5-triazines and the oxazines; and the substituted derivatives thereof, said substituents being selected from the group consis-ting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl group, aryl-carbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; (4) a condensed aromatic ring having the formula wherein A represents the atoms necessary to form an aromatic condensed ring system.

16. The photographic light-sensitive element as claimed in claim 14 wherein said Z is selected from the group consisting of

Claim 16 continued . . .

, , , , and wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33 and R34 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

17. The photographic light-sensitive element as claimed in claim 14 wherein R1 is a group represented by the formula:

and R2 is a group represented by the formula:

Claim 17 continued ...
wherein X is a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, and Y1, Y2 and Y3, which may be the same or different, are each selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl. groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfon-amido groups, amino groups, nitro groups, and cyano groups, Y4 and Y8, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups and alkoxy groups, Y5, Y6 and Y7, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups and acylamino groups; and Z is selected from the group consisting of , , , , , and

Claim 17 continued ...

wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33 and R34 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

18. A photographic light-sensitive element comprising a support coated thereon at least one silver halide emulsion layer containing a yellow dye forming coupler having the general formula:

wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group and Z is selected from the group consisting of , , , ,

Claim 18 continued ...

and wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33 and R34 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

19. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline in the solution containing an aromatic primary amino developing agent presence of a yellow dye forming coupler having the following general formula:

wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group and Z represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a five- or six-membered ring.

20. A method for forming dye images comprising exposing a light-sensitive element having on a support a photographic emulsion layer containing a diacylamino substituted yellow dye forming coupler of the general formula wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group and Z represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a five- or six-membered ring, and wherein at least one of R1, R2 or Z contains as a substituent a hydrophobic group of from about 8 to about 32 carbon atoms, and processing the exposed element with an aqueous alkaline solution containing an aromatic primary amino developing agent.

21. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow forming coupler having the following general formula wherein R1 represents (1) a phenyl group; (2) a substituted phenyl group, wherein said substituents are one or more members from the group consisting of halogen atoms, alkyl groups, alkenyl groups, Claim 21 continued...
alkoxy groups, aryl group, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxy carbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino. groups, ureido groups, sulfon-amido groups, amino groups, nitro groups, cyano groups and hydroxyl group; or (3) a condensed aromatic ring having the formula wherein A represents the atoms necessary to form an aromatic condensed ring system; R2 represents (1) a phenyl group; (2) a substituted phenyl group, wherein said substituents are one or more members from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, arylcarbonyl groups, alkylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups; (3) a heterocyclic group bound to said group in the general formula through a carbon atom in said heterocyclic group which is part of the conjugated electron system and selected from the group consisting of the thiophenes, furans, pyrans, chromenes, pyrroles, pyridines, pyrazines, pyrimidines, pyridazines, indolidines, perimidines, thiazoles, imidazoles, oxazoles, 1,3,5-triazines and the oxazines; and the substituted derivatives thereof, said substituents being selected from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups,

Claim 21 continued...
alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups, cyano groups and hydroxyl groups: (4) a condensed aromatic ring having the formula wherein A represents the atoms necessary to form an aromatic condensed ring system; and Z represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a five- or six-membered ring.

22. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula wherein R1 is an aryl group, R2 is an aryl group or a heterocyclic group, and Z is selected from the group consisting of , , ,

Claim 22 contd...

, , , and wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33 and R34 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R16 and R17, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl gorup or an aryl group, and W is an oxygen atom or a sulfur atom.

23. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula Claim 23 contd....

wherein Z is selected from the group consisting , , , , , , , , , and wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R3 , R33 and R34 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or

Claim 23 contd....

unsaturated 5-membered or 6-membered ring, wherein R21, R26, R35, R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

24. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula wherein R1 is an aryl group, R2 is an aryl group or a hetero-cyclic group and Z is selected from the group consisting of , , , , , , , , ,

Claim 24 contd.....

and wherein R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R22, R23, R24, R25, R27, R28, R29, R30, R31, R32, R33 and R34 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfo group or a carboxyl group, wherein R3 and R5, R7 and R8, R9 and R11, R12 and R13, R15 and R16, R17 and R18, R24 and R25, R31 and R32 may be combined together to form a saturated or unsaturated 5-membered or 6-membered ring, wherein R21, R26, R35 R36 and R37 each represents a hydrogen atom, an alkyl group or an aryl group, and W is an oxygen atom or a sulfur atom.

25. The photographic light-sensitive element as claimed in claim 2 wherein R1 is a group represented by the formula and R2 is a group represented by the formula wherein X is a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, and Y1, Y2 and Y3, which may be the same or different, are each selected from the group consisting

Claim 25 contd...

of hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups and cyano groups, Y4 and Y8, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups and alkoxy groups, Y5, Y6 and Y7, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups and acylamino groups; and Z represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a four-, five- or six-membered ring.

26. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula wherein X is a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, and Y1, Y2 and Y3, which may be the Claim 25 contd...

same or different, are each selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups and cyano groups, Y4 and Y8, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups and alkoxy groups, Y5, Y6 and Y7, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups and acylamino groups and Z
represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a four-, five- or six-membered ring.

27. The photographic light-sensitive element as claimed in claim 14 wherein R1 is a group represented by the formula and R2 is a group represented by the formula

Claim 27 contd.....

wherein X is a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, and Y1, Y2 and Y3, which may be the same or different, are each selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups and cyano groups, Y4 and Y8, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups and alkoxy groups, Y5, Y6 and Y7, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups and acylamino groups; and Z
represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a five-or six-membered ring.

28. A method for forming dye images comprising processing a silver halide photographic emulsion with an aqueous alkaline solution containing an aromatic primary amino developing agent in the presence of a yellow dye forming coupler having the following general formula

Claim 28 contd ...

wherein X is a halogen atom, an alkoxy group, an aryloxy group or a tertiary amino group, and Y1, Y2 and Y3, which may be the same or different, are each selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxyl groups, alkoxycarbonyl groups, carbamyl groups, sulfo groups, sulfamyl groups, acylamino groups, ureido groups, sulfonamido groups, amino groups, nitro groups and cyano groups, Y4 and Y8, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups and alkoxy group, Y5, Y6 and Y7, which may be the same or different, are each selected from the group consisting of hydrogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups, alkylamino groups and acylamino groups; and Z
represents the nonmetallic atom or atoms necessary to form, together with the moiety in the general formula, a five- or six-membered ring.

29. A method for forming dye images comprising exposing the photographic light-sensitive element of Claim 1, developing the exposed element with an aqueous alkaline solution containing an aromatic primary amino developing agent and blixing the developed element with a blix solution containing a silver oxidizing agent and a silver halide solvent.

30. The method for forming dye images of Claim 29, wherein the silver oxidizing agent is a ferric complex of ethylenediamine-tetraacetic acid.